Block copolymer

ABSTRACT

Provided are a block copolymer including a polymer block containing acrylonitrile or methacrylonitrile as a principal constituent, which is excellent in heat resistance, weatherability, oil resistance, flame retardancy, and low-temperature resistance and which can be economically produced; and a thermoplastic resin composition and an elastomer composition each containing the block copolymer. The block copolymer is produced by reversible addition-fragmentation chain transfer polymerization in the presence of a thiocarbonylthio group-containing compound.

RELATED APPLICATION

This application is a nationalization of PCT application PCT/JP02/06656filed on Jul. 1, 2002, claiming priority to Japanese Application No.2001-215707 filed on Jul. 16, 2001 and Japanese Application No.2001-230295 filed on Jul. 30, 2001.

TECHNICAL FIELD

The present invention relates to block copolymers. More particularly,the invention relates to a block copolymer including a polymer blockwhich contains a monomer selected from the group consisting ofacrylonitrile and methacrylonitrile as a principal constituent.Furthermore, the present invention relates to a thermoplastic resincomposition or elastomer composition containing the block copolymer asan essential component.

BACKGROUND ART

Materials in which acrylonitrile or methacrylonitrile is polymerizedhave been widely used because of their excellent heat resistance,weatherability, oil resistance, flame retardancy, etc. Commonly knownexamples thereof include acrylonitrile-styrene-acrylic rubber copolymerresins (AAS), acrylonitrile-ethylene-styrene copolymer resins (AES),acrylonitrile-styrene copolymer resins (AS),acrylonitrile-butadiene-styrene copolymer resins (ABS),acrylonitrile-chlorinated polyethylene-styrene resins (ACS),acrylonitrile-butadiene copolymer rubber (NBR), and hydrogenated nitrilerubber.

However, all of these materials are formed by random copolymerization ofacrylonitrile and other monomers or by graft copolymerization ofacrylonitrile onto polymer chains. With respect to block copolymersincluding polymer blocks containing acrylonitrile and methacrylonitrileas principal constituents, although research has been conducted on thelaboratory level, no production has been performed industrially.

In general, in an acrylonitrile-containing polymer, as the acrylonitrilecontent is increased, oil resistance, wear resistance, heat resistance,and strength are improved, while low-temperature resistance tends to bedegraded. In contrast, in a block copolymer in which a polymer blockcontaining acrylonitrile or methacrylonitrile as a principal constituentand a flexible polymer block composed of other constituents,low-temperature resistance is considered to be improved whilemaintaining excellence in heat resistance, oil resistance, etc.

As the methods for synthesizing block copolymers, living polymerizationmethods are usually used. Examples of living polymerization methodsinclude living cationic polymerization methods, living anionicpolymerization methods, and living radical polymerization methods. Amongthem, living radical polymerization methods are most useful because ofthe applicability to a wide variety of monomers and also because of theapplicability to water-based polymerization. Commonly known examples ofthe living radical polymerization methods include a method usingnitroxyl radicals, such as 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)radicals, described in Junpo He et al., Polymer, 2000, 41, p. 4573; andan atom transfer radical polymerization method described inMatyjaszewski et al., J. Am. Chem. Soc., 1995, 117, p. 5614. However, inthe method using nitroxyl radicals, little has been reported about thepolymerization of monomers other than styrene, and no example has beenknown about the polymerization of acrylonitrile. Furthermore, ingeneral, since the polymerization temperature must be 120° C. or more,this method is not economical for industrial production. On the otherhand, in the atom transfer radical polymerization, since nitrile groupscoordinate to a metal complex which is a catalyst, polymerization doesnot proceed satisfactorily. Furthermore, a complicated purification stepis required in order to remove the metal complex from the polymer, thusbeing uneconomical. Additionally, in the living radical polymerizationmethods described above, it is generally difficult to performwater-based polymerization, such as emulsion polymerization orsuspension polymerization. In the living radical polymerization methodsdescribed above, there are cases in which it is difficult to performwater-based polymerization, such as emulsion polymerization orsuspension polymerization.

DISCLOSURE OF INVENTION

The present invention has been achieved to overcome the problemsassociated with the conventional techniques. It is an object of thepresent invention to provide a block copolymer including a polymer blockcontaining acrylonitrile or methacrylonitrile as a principalconstituent, which is excellent in heat resistance, weatherability, oilresistance, flame retardancy, and low-temperature resistance and whichcan be economically produced. It is another object of the presentinvention to provide a thermoplastic resin composition or elastomercomposition containing the block copolymer.

A block copolymer of the present invention includes a polymer block (A)and a polymer block (B), the block copolymer being produced by formingthe polymer block (A) by reversible addition-fragmentation chaintransfer polymerization in the presence of a thiocarbonylthiogroup-containing compound, and then by forming the polymer block (B).

The polymer block (A) is prepared by (co)polymerizing 50% to 100% byweight of at least one monomer selected from the group consisting ofacrylonitrile and methacrylonitrile and 50% to 0% by weight of at leastone monomer selected from the group consisting of methacrylate esters,styrene, and α-methylstyrene.

The polymer block (B) is prepared by (co)polymerizing at least onemonomer selected from the group consisting of acrylic acid, methacrylicacid, acrylate esters, methacrylate esters, vinyl acetate, styrene,α-methylstyrene, butadiene, isoprene, and vinyl chloride.

A block copolymer of the present invention may be produced by separatelyforming the polymer block (A) and the polymer block (B), each by areversible addition-fragmentation chain transfer polymerization methodin the presence of a thiocarbonylthio group-containing compound, andthen by coupling the polymer block (A) and the polymer block (B).

The block copolymer of the present invention can be of various types.Examples of types include, but are not limited to, an A-B diblockcopolymer including the polymer block (A) and the polymer block (B), anA-B-A triblock copolymer, a B-A-B triblock copolymer, an (A-B)nmultiblock copolymer, and a branched block copolymer. Polymers producedby linking monomers other than the ones described above to such polymersmay also be acceptable. Examples thereof include an A-B-C polymerincluding a polymer chain C formed by a monomer other than the onesdescribed above.

The block copolymer of the present invention is produced by a reversibleaddition-fragmentation chain transfer (RAFT) method in the presence of athiocarbonylthio group-containing compound. RAFT polymerization methodsare disclosed, for example, in PCT Publication No. WO98/01478; PCTPublication No. WO99/05099; PCT Publication No. WO99/31144;Macromolecules, 1998, 31, p. 5559; Macromolecules, 1999, 32, p. 2071;Macromolecules, 1999, 32, p. 6977; and Macromolecules, 2000, 33, p. 243.

That is, the monomers for forming the polymer block (A) are polymerizedin the presence of a thiocarbonylthio group-containing compound to formthe polymer block (A). The monomers for forming the polymer block (B)are then polymerized to form the polymer block (B) linked to the polymerblock (A). Thereby, a block copolymer including the polymer block (A)and the polymer block (B) is produced. In this method, thethiocarbonylthio group-containing compound functions as a chain transferagent, and the resultant block copolymer contains at least onethiocarbonylthio group in each molecule. The block copolymers includingthe polymer blocks (A) and the polymer blocks (B) are, as necessary,subjected to a coupling reaction to produce a triblock copolymer, suchas the A-B-A or B-A-B type; or a multiblock copolymer, such as the(A-B)n type. It is also possible to produce a block copolymer by formingthe polymer block (A) and the polymer block (B) separately, each in thepresence of a thiocarbonylthio group-containing compound, and then bycoupling the polymer block (A) and the polymer block (B).

When the block copolymers, or the polymer blocks (A) and (B), arecoupled to each other, the block copolymers preferably have functionalgroups at the ends in view of the fact that coupling can be performedeasily and reliably. In the present invention, the thiocarbonylthiogroups introduced into the polymer by the method described above can beused as such functional groups.

When the thiocarbonylthio group-containing copolymers are subjected to acoupling reaction, for example, first, the copolymers are allowed toreact with a processing agent composed of at least one compound selectedfrom the group consisting of bases, acids, and hydrogen-nitrogenbond-containing compounds to convert the thiocarbonylthio groups of thecopolymers into mercapto groups or mercaptide groups. Next, coupling ofthe copolymers is performed using the mercapto groups or mercaptidegroups. The block copolymer with the desired type is thereby obtained.

The polymer block (A) is prepared by (co)polymerizing 50% to 100% byweight of at least one monomer selected from the group consisting ofacrylonitrile and methacrylonitrile and 50% to 0% by weight of at leastone monomer selected from the group consisting of methacrylate esters,styrene, and α-methylstyrene.

Because of the excellence in oil resistance and flame retardancy of theresultant block copolymer, the polymer block (A) is prepared preferablyby polymerizing 80% to 100% of at least one monomer selected from thegroup consisting of acrylonitrile and methacrylonitrile and 20% to 0% ofat least one monomer selected from the group consisting of methacrylateesters, styrene, and α-methylstyrene, and more preferably bypolymerizing 100% by weight of at least one monomer selected from thegroup consisting of acrylonitrile and methacrylonitrile. With respect tothe amounts of acrylonitrile and methacrylonitrile used, in view ofavailability and cost, preferably 50% by weight or more of acrylonitrileis polymerized, more preferably 80% by weight or more of acrylonitrileis polymerized, and most preferably 100% by weight of acrylonitrile ispolymerized.

In view of the strength and workability of the resultant blockcopolymer, the molecular weight distribution, which is determined by gelpermeation chromatography analysis, of the polymer block (A) ispreferably 1.8 or less, and more preferably 1.5 or less. In the presentinvention, the molecular weight distribution (Mw/Mn) is a valuecorresponding to the ratio of the weight-average molecular weight (Mw)to the number-average molecular weight (Mn) determined by gel permeationchromatography analysis.

In view of the strength and workability of the resultant blockcopolymer, the number-average molecular weight of the polymer block (A)is preferably in the range of 1,000 to 500,000, and more preferably inthe range of 3,000 to 100,000.

Because of the excellence in heat resistance and strength of theresultant block copolymer, the glass transition temperature of thepolymer block (A) is preferably 50° C. or more, and more preferably 80°C. or more. In the present invention, the glass transition temperature(Tg) is determined according to the following equation:(1/Tg)=(W ₁ /Tg ₁)+(W ₂ /Tg ₂)+ . . . +(W _(m) /Tg _(m))(wherein Tg₁, Tg₂, . . . , Tg_(m) are the glass transition temperaturescorrespond to monomers used for polymerization when they arehomopolymerized, respectively; W₁, W₂, . . . , W_(m) are the weightfractions of the monomer components used for polymerization in thepolymer block, respectively; and the relationship W₁+W₂+ . . . W_(m)=1is satisfied). Additionally, the above equation is generally known asthe Fox equation. With respect to the glass transition temperatures ofthe individual homopolymers (Tg₁, Tg₂, . . . , Tg_(m)), for example, thevalues described in Polymer Handbook Third Edition (Wiley-Interscience,1989) may be used.

Among the monomers constituting the polymer block (A), as at least onemonomer selected from the group consisting of methacrylate esters,styrene, and α-methylstyrene, because of the excellence in oilresistance, weatherability, and heat resistance, methacrylate esters arepreferable. Examples of such methacrylate esters include, but are notlimited to, alkyl esters, aryl esters, and aralkyl esters of methacrylicacid. Examples of methacrylate esters include, but are not limited to,methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutylmethacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate,tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate,benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropylmethacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate,tetrahydrofurfuryl methacrylate, ethylene glycol dimethacrylate,triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate,1,3-butylene glycol dimethacrylate, trimethylolpropane trimethacrylate,isopropyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptylmethacrylate, octyl methacrylate, nonyl methacrylate, decylmethacrylate, dodecyl methacrylate, phenyl methacrylate, tolylmethacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate,3-methoxybutyl methacrylate, 2-aminoethyl methacrylate,2-methacryloyloxypropyltrimethoxysilane,2-methacryloyloxypropyldimethoxymethylsilane, trifluoromethylmethacrylate, pentafluoroethyl methacrylate, 2-aminoethyl methacrylate,2-(N,N-dimethylamino)ethyl methacrylate, 3-aminopropyl methacrylate,3-(N,N-diethylamino)propyl methacrylate, and 2,2,2-trifluoroethylmethacrylate. These compounds may be used alone or in combination. Amongthese methacrylate esters, because of the excellence in heat resistance,weatherability, oil resistance, and strength of the resultantcopolymers, methacrylate esters of alcohols containing 4 or less carbonatoms, such as methyl methacrylate, ethyl methacrylate, and n-butylmethacrylate, are preferable, and methyl methacrylate is particularlypreferable.

Additionally, by adding methacrylate esters having functional groups,when the resultant block copolymers are molded, crosslinking reactionscan be carried out using the functional groups. Thereby, molded objectshaving excellent strength and compression set can be produced. It isalso possible to produce molded objects having excellent compatibilitywith various resins and rubbers using the functional groups. Examples ofsuch functional groups include, but are not limited to, a hydroxylgroup, an amino group, an epoxy group, a carboxyl group, and acrosslinkable silyl group. Examples of the methacrylate esterscontaining such functional groups include, but are not limited to,hydroxyl group-containing methacrylate esters, such as 2-hydroxyethylmethacrylate and 2-hydroxypropyl methacrylate, amino group-containingmethacrylate esters, such as 2-aminoethyl methacrylate and 3-aminopropylmethacrylate; epoxy group-containing methacrylate esters, such asglycidyl methacrylate; carboxyl group-containing methacrylate esters,such as 3-methacryloyloxypropanoic acid and 4-methacryloyloxybenzoicacid; and crosslinkable silyl group-containing methacrylate esters, suchas 2-methacryloyloxypropyltrimethoxysilane and2-methacryloyloxypropyldimethoxymethylsilane. Alternatively, after themonomers are polymerized, carboxyl groups may be introduced byhydrolysis. These methacrylate esters may be used alone or incombination. If the content of the functional group-containingmethacrylate ester is too high, it may be brittle when the blockcopolymer is formed and crosslinked. Therefore, the content of thefunctional group-containing methacrylate ester is preferably less than10% by weight, and more preferably less than 5% by weight, of thepolymer block (A). However, this does not apply to the case whenfunctional groups are introduced in order to improve compatibility withvarious resins, rubbers, etc.

As described above, the polymer block (B) in the block copolymer of thepresent invention is composed of at least one monomer selected from thegroup consisting of acrylic acid, methacrylic acid, acrylate esters,methacrylate esters, vinyl acetate, styrene, α-methylstyrene, butadiene,isoprene, and vinyl chloride. These monomers may be used alone or incombination. Additionally, after the polymerization, the vinyl acetateunit may be saponified, the butadiene unit or isoprene unit may behydrogenated, or the butadiene unit, isoprene unit, or vinyl chlorideunit may be chlorinated.

Among the monomers constituting the polymer block (B), examples ofacrylate esters include, but are not limited to, alkyl esters, arylesters, and aralkyl esters of acrylic acid. Examples of acrylate estersinclude, but are not limited to, methyl acrylate, ethyl acrylate,n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, hexyl acrylate,2-ethylhexyl acrylate, cyclohexyl acrylate, octyl acrylate, decylacrylate, dodecyl acrylate, phenyl acrylate, tolyl acrylate, benzylacrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutylacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, stearylacrylate, glycidyl acrylate, 2-acryloyloxypropyldimethoxymethylsilane,2-acryloyloxypropyltrimethoxysilane, trifluoromethyl acrylate,pentafluoroethyl acrylate, 2,2,2-trifluoroethyl acrylate,3-dimethylaminoethyl acrylate, isobutyl acrylate, 4-hydroxybutylacrylate, tert-butyl acrylate, acrylate of alkyl-modifieddipentaerythritol, ethylene oxide-modified bisphenol A diacrylate,carbitol acrylate, acrylate of ε-caprolactone-modifieddipentaerythritol, caprolactone-modified tetrahydrofurfuryl acrylate,diacrylate of caprolactone-modified neopentyl glycol hydroxypivalate,ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate,dipentaerythritol pentaacrylate, tetraethylene glycol acrylate,tetrahydrofurfuryl acrylate, tripropylene glycol acrylate,trimethylolpropane ethoxy triacrylate, trimethylolpropane triacrylate,neopentyl glycol diacrylate, diacrylate of neopentyl glycolhydroxypivalate, 1,9-nonandiol acrylate, 1,4-butanediol acrylate,2-propanoic acid[2-[1,1-dimethyl-2-[(1-oxo-2-propenyl)oxy]ethyl]-5-ethyl-1,3-dioxane-5-yl]methylester, 1,6-hexanediol acrylate, pentaerythritol triacrylate,2-acryloyloxypropylhydrogen phthalate, methyl 3-methoxyacrylate,2-aminoethyl acrylate, 2-(N,N-dimethylamino)ethyl acrylate,3-aminopropyl acrylate, 3-(N,N-diethylamino)propyl acrylate, and allylacrylate.

Among the monomers constituting the polymer block (B), the methacrylateester is not particularly limited. Examples of methacrylate esters arethe same as those described above with reference to the polymer block(A).

Among the monomers constituting the polymer block (B), in view of heatresistance and weatherability, acrylate esters and methacrylate estersare preferable; in view of flexibility, acrylate esters are preferable;and in view of availability and cost, acrylate esters of alcoholscontaining 4 or less carbon atoms, such as ethyl acrylate, n-propylacrylate, n-butyl acrylate, and tert-butyl acrylate are more preferable.When the block copolymers of the present invention are used as textiles,in view of texture, surface properties, and flame retardancy, vinylchloride is preferably used. When the block copolymers of the presentinvention are used as modifiers for polar resins, such as polyesterresins and polycarbonate resins, preferred monomers for use are asfollows: acrylic acid, methacrylic acid, functional group-containingacrylate esters and functional group-containing methacrylate esters,such as hydroxyl group-containing acrylate esters, hydroxylgroup-containing methacrylate esters, amino group-containing acrylateesters, amino group-containing methacrylate esters, carboxylgroup-containing acrylate esters, carboxyl group-containing methacrylateesters, epoxy group-containing acrylate esters, epoxy group-containingmethacrylate esters, silyl group-containing acrylate esters, and silylgroup-containing methacrylate esters.

The monomers constituting the polymer block (B) are preferably selectedbased on the following criteria. For example, because of the excellencein flexibility and low-temperature resistance of the resultant blockcopolymer, the glass transition temperature of the polymer prepared bypolymerizing the monomers only is 30° C. or less, and more preferably 0°C. or less. The glass transition temperature of the polymer block (B) isdetermined according to the Fox equation as in the polymer block (A).

In view of the strength and workability of the resultant blockcopolymer, the molecular weight distribution, which is determined by gelpermeation chromatography analysis, of the polymer prepared bypolymerizing only the monomers constituting the polymer block (B) ispreferably 1.8 or less, and more preferably 1.5 or less.

Furthermore, in view of flexibility and elasticity, the number-averagemolecular weight, which is determined by gel permeation chromatographyanalysis, of the polymer prepared by polymerizing only the monomersconstituting the polymer block (B) is preferably in the range of 1,000to 1,000,000, more preferably in the range of 3,000 to 500,000, and mostpreferably in the range of 5,000 to 200,000.

As described above, the block copolymer of the present invention isproduced by forming the polymer block (A) and then by forming thepolymer block (B), and furthermore by coupling them to each other.Alternatively, the polymer block (A) and the polymer block (B) areformed separately, and then coupling is performed. In view ofworkability and the excellence in compatibility when the block copolymeris mixed with resins, rubbers, or the like, the molecular weightdistribution, which is determined by gel permeation chromatographyanalysis, of the block copolymer is preferably 1.8 or less, and morepreferably 1.6 or less.

The thiocarbonylthio group-containing compound used as a chain transferagent in the radical polymerization described above is at least onecompound selected from the group consisting of a compound represented bygeneral formula (1):

(wherein R¹ is a p-valent organic group of 1 or more carbon atoms whichmay contain one of nitrogen, oxygen, sulfur, halogen, silicon,phosphorus, and metal atoms, or which may be a polymer; Z¹ is a hydrogenatom, halogen atom, or monovalent organic group of 1 or more carbonatoms which may contain one of nitrogen, oxygen, sulfur, halogen,silicon, and phosphorus atoms, or which may be a polymer; when pluralZ¹s are present, the plural Z¹s may be the same or different; and p isan integer of 1 or more), and a compound represented by general formula(2):

(wherein R² is a monovalent organic group of 1 or more carbon atomswhich may contain one of nitrogen, oxygen, sulfur, halogen, silicon,phosphorus, and metal atoms, or which may be a polymer; Z² is an oxygenatom (when q=2), sulfur atom (when q=2), nitrogen atom (when q=3), orq-valent organic group of 1 or more carbon atoms which may contain oneof nitrogen, oxygen, sulfur, halogen, silicon, and phosphorus atoms, orwhich may be a polymer; plural R²s may be the same or different; and qis an integer of 2 or more).

In the compound having the thiocarbonylthio structure represented bygeneral formula (1), R¹ is not particularly limited. In view ofavailability of the compound, preferably, R¹ has 1 to 20 carbon atoms,and p is 6 or less. Examples of R¹ include alkyl, substituted alkyl,aralkyl, substituted aralkyl, a polyvalent aliphatic hydrocarbon group,a polyvalent aromatic hydrocarbon group, a polyvalent aliphatichydrocarbon group with an aromatic ring, a polyvalent aromatichydrocarbon group with an aliphatic group, a polyvalent aliphatichydrocarbon group containing a heteroatom, and a polyvalent aromaticsubstituted hydrocarbon group containing a heteroatom. In view, ofavailability of the compound and polymerization activity, R¹ ispreferably benzyl, 1-phenylethyl, 2-(2-phenylpropyl), 1-acetoxyethyl,1-(4-methoxyphenyl)ethyl, ethoxycarbonylmethyl,2-(2-ethoxycarbonylpropyl), 2-(2-cyanopropyl), tert-butyl,1,1,3,3-tetramethylbutyl, 2-(2-(p-chlorophenyl)propyl), vinylbenzyl,tert-butylthio, 2-carboxylethyl, carboxylmethyl, cyanomethyl,1-cyanoethyl, 2-(2-cyanobutyl), or any one of organic groups representedby the following formulae.

(In the formulae, n is an integer of 1 or more, and r is an integer of 0or more.)

(In the formulae, R⁴ is a divalent organic group of 1 or more carbonatoms; n is an integer of 1 or more; r is an integer of 0 or more; andplural r's may be the same or different.)

(In the formulae, n is an integer of 1 or more; r is an integer of 0 ormore; and plural r's may be the same or different.)

In the above formulae, in view of availability of the compound,preferably, each of n and r is 500 or less. Preferably, R⁴ has 1 to 20carbon atoms. Examples of R⁴ structures include, but are not limited to,—(CH₂)_(n)— (wherein n is an integer of 1 or more), —C₆H₄—, and—CH₂—C₆H₄—CH₂—.

In the compound having the thiocarbonylthio structure represented bygeneral formula (1), Z¹ is not particularly limited. In view ofavailability of the compound and polymerization activity, when Z¹ is anorganic group, preferably, the organic group has 1 to 20 carbon atoms.Examples of Z¹ include alkyl, substituted alkyl, alkoxy, aryloxy, aryl,substituted aryl, aralkyl, substituted aralkyl, heterocyclic,N-aryl-N-alkylamino, N,N-diarylamino, N,N-dialkylamino, thioalkyl, anddialkyiphosphinyl groups. In view of availability of the compound, Z¹ ispreferably phenyl, methyl, ethyl, benzyl, 4-chlorophenyl, 1-naphthyl,2-naphthyl, diethoxyphosphinyl, n-butyl, tert-butyl, methoxy, ethoxy,methylthio, phenoxy, phenylthio, N,N-dimethylamino, N,N-diethylamino,N-phenyl-N-methylamino, N-phenyl-N-ethylamino, benzylthio,pentafluorophenoxy, or any one of organic groups represented by formulaebelow.

In the compound having the thiocarbonylthio structure represented bygeneral formula (2), R² is not particularly limited. In view ofavailability of the compound and polymerization activity, preferably, R²has 1 to 20 carbon atoms. Examples of R² include alkyl, substitutedalkyl, aralkyl, and substituted aralkyl. In view of availability of thecompound, R² is preferably benzyl, 1-phenylethyl, 2-(2-phenylpropyl),1-acetoxyethyl, 1-(4-methoxyphenyl)ethyl, ethoxycarbonylmethyl,2-(2-ethoxycarbonylpropyl), 2-(2-cyanopropyl), tert-butyl,1,1,3,3-tetramethylbutyl, 2-(2-(p-chlorophenyl)propyl), vinylbenzyl,tert-butylthio, 2-carboxylethyl, carboxylmethyl, cyanomethyl,1-cyanoethyl, 2-(2-cyanobutyl), or any one of organic groups representedby formulae below, (wherein n is an integer of 1 or more, and r is aninteger of 0 or more).

In the above formulae, each of n and r is preferably 500 or less in viewof availability of the compound.

In the compound having the thiocarbonylthio structure represented bygeneral formula (2), Z² is not particularly limited. In view ofavailability of the compound and polymerization activity, when Z² is anorganic group, preferably, the organic group has 1 to 20 carbon atoms,and q is 6 or less. Examples of Z² include a polyvalent aliphatichydrocarbon group, a polyvalent aromatic hydrocarbon group, a polyvalentaliphatic hydrocarbon group with an aromatic ring, a polyvalent aromatichydrocarbon group with an aliphatic group, a polyvalent aliphatichydrocarbon group containing a heteroatom, and a polyvalent aromaticsubstituted hydrocarbon group containing a heteroatom. In view ofavailability of the compound, preferably Z² has any one of thestructures represented by formulae below, (wherein n is an integer of 1or more, and r is an integer of 0 or more).

In the above formulae, each of n and r is preferably 500 or less in viewof availability of the compound.

Among the thiocarbonylthio group-containing compounds used in thepresent invention, in view of availability and the fact that A-B diblockcopolymers can be easily synthesized, preferred is a compoundrepresented by general formula (3):

(wherein R² is a monovalent organic group of 1 or more carbon atomswhich may contain one of nitrogen, oxygen, sulfur, halogen, silicon,phosphorus, and metal atoms, or which may be a polymer; and Z¹ is ahydrogen atom, halogen atom, or monovalent organic group of 1 or morecarbon atoms which may contain one of nitrogen, oxygen, sulfur, halogen,silicon, and phosphorus atoms, or which may be a polymer). In view ofavailability of the compound and polymerization activity, preferably, R²has 1 to 20 carbon atoms. The specific examples of the structures of R²and Z¹ in the formula are the same as those described with reference toR² in general formula (2) and Z¹ in general formula (1), respectively.

In the present invention, when the polymer blocks (A) and (B) aresynthesized separately and then are coupled to each other to produce anA-B-A triblock copolymer, because of ease in production, preferably, acompound represented by general formula (3) is used as thethiocarbonylthio group-containing compound used for the preparation ofthe polymer block (A); and a compound represented by general formula (4)below is used as the thiocarbonylthio group-containing compound used forthe preparation of the polymer block (B):

(wherein R³ is a divalent organic group of 1 or more carbon atoms whichmay contain one of nitrogen, oxygen, sulfur, halogen, silicon,phosphorus, and metal atoms, or which may be a polymer; each Z¹ is ahydrogen atom, halogen atom, or monovalent organic group of 1 or morecarbon atoms which may contain one of nitrogen, oxygen, sulfur, halogen,silicon, and phosphorus atoms, or which may be a polymer; and two Z¹smay be the same or different). Specific examples of Z¹ structures in theformula are the same as those described with reference to Z¹ in generalformula (1).

In the thiocarbonylthio group-containing compound represented by generalformula (4), preferably, R³ has 1 to 20 carbon atoms. Although R³ is notparticularly limited, in view of availability and polymerizationactivity, preferably, R³ has any one of the structures represented byformulae below.

(In the above formulae, R⁴ is a divalent organic group of 1 or morecarbon atoms; n is an integer of 1 or more; r is an integer of 0 ormore; and plural r's may be the same or different.)

In the above formulae, each of n and r is preferably 500 or less in viewof availability of the compound. Preferably, R⁴ has 1 to 20 carbonatoms. Examples of R⁴ structures include, but are not limited to,—(CH₂)_(n)— (wherein n is an integer of 1 or more), —C₆H₄—, and—CH₂—C₆H₄—CH₂—.

Specific examples of compounds having the thiocarbonylthio structures,which are used in the present invention, include, but are not limitedto, compounds represented by formulae below, (wherein Me, Et, Ph, and Acrepresent methyl, ethyl, phenyl, and acetyl, respectively; R⁴ is adivalent organic group of 1 or more carbon atoms; n is an integer of 1or more; r is an integer of 0 or more; and plural r's may be the same ordifferent).

In the above formulae, each of n and r is preferably 500 or less in viewof availability of the compound. Preferably, R⁴ has 1 to 20 carbonatoms. Examples of R⁴ structures include, but are not limited to,—(CH₂)_(n)— (wherein n is an integer of 1 or more), —C₆H₄—, and—CH₂—C₆H₄—CH₂—.

The amount of the thiocarbonylthio group-containing compound used in thepresent invention is not particularly limited and can bestoichiometrically calculated based on the monomers used. In general,since the number of moles of the resultant polymer is substantiallyequal to the number of moles of the thiocarbonylthio group-containingcompound, the molecular weight of the polymer can be controlled byadjusting the molar ratio of the monomers to the thiocarbonylthiogroup-containing compound. When the rate of reaction of the monomers is100%, the theoretical molecular weight of the resultant polymer isrepresented by (x/y)×Mm+Mr, wherein Mm is the molecular weight of themonomers used, x is the number of moles of the monomers used, Mr is themolecular weight of the thiocarbonylthio group-containing compound, andy is the number of moles of the thiocarbonylthio group-containingcompound used. Consequently, the amount of the thiocarbonylthiogroup-containing compound used may be calculated based on thenumber-average molecular weight of the desired polymer.

The technique used for radical polymerization is not particularlylimited when the block copolymer of the present invention is prepared.Any method commonly used in the art, such as bulk polymerization,solution polymerization, emulsion polymerization, suspensionpolymerization, or microsuspension polymerization, may be employed.Among them, in view of cost and safety, water-based polymerization, suchas emulsion polymerization, suspension polymerization, ormicrosuspension polymerization, is preferred.

In the case of solution polymerization of the monomers, examples ofsolvents which may be used include, but are not limited to, hydrocarbonsolvents, such as heptane, hexane, octane, and mineral spirit; estersolvents, such as ethyl acetate, n-butyl acetate, isobutyl acetate,ethylene glycol monomethyl ether acetate, and diethylene glycolmonobutyl ether acetate; ketone solvents, such as acetone, methyl ethylketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone;alcohol solvents, such as methanol, ethanol, isopropanol, n-butanol,sec-butanol, and isobutanol; ether solvents, such as tetrahydrofuran,diethyl ether, dibutyl ether, dioxane, ethylene glycol dimethyl ether,and ethylene glycol diethyl ether; amide solvents, such asdimethylformamide, diethylformamide, dimethylacetamide, anddiethylacetamide; and aromatic petroleum solvents, such as toluene,xylene, benzene, Swasol 310 (manufactured by Cosmo Oil Co., Ltd.),Swasol 1000 (manufactured by Cosmo Oil Co., Ltd.), and Swasol 1500(manufactured by Cosmo Oil Co., Ltd.). These solvents may be used aloneor in combination. The types and amounts of solvent used may bedetermined in consideration of the solubility of the monomers used, thesolubility of the resultant polymer, the polymerization initiatorconcentration and the monomer concentration suitable for achieving asatisfactory reaction rate, the solubility of the thiocarbonylthiogroup-containing compound, effects on human body and environment,availability, cost, etc., and are not particularly limited. In view ofsolubility, availability, and cost, industrially, toluene,dimethylformamide, tetrahydrofuran, and acetone are preferable, anddimethylformamide and toluene are more preferable.

In the present invention, in the case of emulsion polymerization ormicrosuspension polymerization of the monomers, examples of emulsifierswhich may be used include, but are not limited to, anionic surfactants,such as fatty acid soap, rosin acid soap, sodiumnaphthalenesulfonate-formalin condensates, sodium alkylsulfonate (e.g.,sodium dodecyl sulfonate), sodium alkylbenzene sulfonate, sodiumalkylsulfate (e.g., sodium dodecyl sulfate), ammonium alkylsulfate,triethanolamine alkylsulfate, sodium dialkylsulfosuccinate, sodiumalkyldiphenylether disulfonate, sodium polyoxyethylene alkyl ethersulfate, and sodium polyoxyethylene alkylphenyl ether sulfate; nonionicsurfactants, such as polyoxyethylene alkyl ether, polyoxyethylene higheralcohol ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fattyacid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fattyacid ester, polyoxyethylene fatty acid ester, polyoxyethyleneaklylamine, and alkyl alkanolamide; and cationic surfactants, such asalkyltrimethylammonium chloride. These emulsifiers may be used alone orin combination. As necessary, a cationic surfactant, such as analkylamine hydrochloride, may be used, or a dispersant for suspensionpolymerization which will be described below may also be added. Theamount of the emulsifier used is not particularly limited. Because ofgood emulsification state and the fact that polymerization proceedssmoothly, the amount of the emulsifier is preferably 0.1 to 20 parts byweight based on 100 parts by weight of the monomers. Among theemulsifiers described above, in view of stability of the emulsificationstate, nonionic surfactants are preferable. Additionally, in order tostabilize the emulsification state, various emulsifying aids may also beused. Examples of emulsifying aids include, but are not limited to,linear hydrocarbons, such as hexadecane; hydrocarbon polymers, such aspolyethylene, polypropylene, polybutadiene, and hydrogenatedpolybutadiene; polar organic solvents, such as acetone, ethanol, andmethanol; and higher alcohols, such as octyl alcohol, decyl alcohol, andlauryl alcohol. The amount of the emulsifying aid used is notparticularly limited. Because of excellence in the balance between costand effect, the amount of the emulsifying aid used is preferably 0.1 to20 parts by weight, and more preferably 0.5 to 15 parts by weight, basedon 100 parts by weight of the emulsifier.

In the case of suspension polymerization of the monomers, any dispersantcommonly used may be used. Examples of dispersants include, but are notlimited to, partially saponified poly(vinyl acetate), poly(vinylalcohol), methyl cellulose, carboxymethyl cellulose, gelatin,poly(alkylene oxide), and combinations of anionic surfactants anddispersing agents. These may be used alone or in combination. Theemulsifier used for emulsion polymerization described above may also beused as necessary. The amount of the dispersant used is not particularlylimited. Because of the fact that polymerization proceeds smoothly, theamount of the dispersant is preferably 0.1 to 20 parts by weight basedon 100 parts by weight of the monomers used.

The polymerization initiator or polymerization initiation method usedfor the radical polymerization is not particularly limited, and anypolymerization initiator or polymerization initiation method commonlyused may be employed. Examples of polymerization initiators include, butare not limited to, peroxide polymerization initiators, such as methylethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanoneperoxide, methyl cyclohexanone peroxide, isobutyryl peroxide,3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, benzoyl peroxide,tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzenehydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutylhydroperoxide, di-tert-butyl peroxide, tert-butyl-α-cumyl peroxide,di-α-cumyl peroxide, 1,4-bis[(tert-butylperoxy)isopropyl]benzene,1,3-bis[(tert-butylperoxy)isopropyl]benzene,2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane,2,5-dimethyl-2,5-bis(tert-butylperoxy)-3-hexyne,1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane,n-butyl-4,4-bis(tert-butylperoxy)valerate,2,2-bis(tert-butylperoxy)butane, tert-butylperoxy acetate,tert-butylperoxy isobutylate, tert-butylperoxy octoate, tert-butylperoxypivalate, tert-butylperoxy neodecanoate,tert-butylperoxy-3,5,5-trimethyl hexanoate, tert-butylperoxy benzoate,tert-butylperoxy laurate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane,bis(2-ethylhexyl)peroxy dicarbonate, diisopropylperoxy dicarbonate,di-sec-butylperoxy dicarbonate, di-n-propylperoxy dicarbonate,bis(3-methoxybutyl)peroxy dicarbonate, bis(2-ethoxyethyl)peroxydicarbonate, bis(4-tert-butylcyclohexyl)peroxy dicarbonate,O-tert-butyl-O-isopropylperoxy carbonate, and succinic acid peroxide;azo polymerization initiators, such as2,2′-azobis-(2-amidinopropane)dihydrochloride, dimethyl2,2′-azobis(isobutyrate),2,2′-azobis-(4-methoxy-2,4-dimethylvaleronitrile),2,2′-azobis(isobutyronitrile), 1,1′-azobis(cyclohexane-1-carbonitrile),azocumene, 2,2′-azobis(2-methylbutyronitrile),2,2′-azobis-(2,4-dimethylvaleronitrile, 4,4′-azobis(4-cyanovalericacid), 2-(tert-butylazo)-2-cyanopropane,2,2′-azobis(2,4,4-trimethylpentane), and 2,2′-azobis(2-methylpropane);inorganic peroxides, such as potassium persulfate and sodium persulfate;vinyl monomers which thermally generate radical species, such asstyrene; compounds which generate radical species by light, such asbenzoin derivatives, benzophenone, acylphosphine oxide, and photo-redoxsystems; and redox polymerization initiators including sodium sulfite,sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid,ferrous sulfate, or the like, as a reducing agent, and potassiumperoxydisulfate, hydrogen peroxide, tert-butyl hydroperoxide, or thelike, as an oxidizing agent. These polymerization initiators may be usedalone or in combination. It may also be possible to use a polymerizationinitiation system by electron irradiation, X-ray irradiation, radiationirradiation, or the like. With respect to polymerization initiationmethods using such initiators, the methods described in Moad and Solomon“The Chemistry of Free Radical Polymerization”, Pergamon, London, 1995,pp. 53–95 may be employed.

In the present invention, the amount of the polymerization initiatorused is not particularly limited. In order to produce a polymer with anarrow molecular weight distribution, the amount of radical speciesgenerated during polymerization is preferably 1 mole or less, and morepreferably 0.5 moles or less, relative to 1 mole of thiocarbonylthiogroup in the thiocarbonylthio group-containing compound. In order tocontrol the amount of radical species generated during polymerization,in addition to the control of the amount of the polymerizationinitiator, preferably, temperature is controlled in the case of thepolymerization initiator which causes thermal dissociation, or theamount of energy is controlled in the case of the polymerizationinitiation system which generates radicals by light or electron beams.Because of ease of control of polymerization, using a polymerizationinitiator which causes thermal dissociation, the polymerization reactionis carried out preferably at temperatures which allow the polymerizationinitiator to have a half-life of 0.5 to 50 hours, more preferably attemperatures which allow the polymerization initiator to have ahalf-life of 1 to 20 hours, and most preferably at temperatures whichallow the polymerization initiator to have a half-life of 5 to 15 hours.

The block copolymer of the present invention is prepared using thesolvent, emulsifier, polymerization initiator, etc., as will bedescribed below.

The thiocarbonylthio group-containing block copolymer is treated with aprocessing agent, as required, so that the thiocarbonylthio groups areconverted into mercapto groups or mercaptide groups. The processingagent used in the process is not particularly limited. In view of highyield, preferably, a method is employed in which the thiocarbonylthiogroup-containing compound is allowed to react with a processing agentcomposed of a compound selected from the group consisting of bases,acids, and hydrogen-nitrogen bond-containing compounds. Among them, whena base or an acid is used, in the presence of water, thiocarbonylthiogroups are converted into mercapto groups by hydrolysis. When ahydrogen-nitrogen bond-containing compound is used, the presence ofwater is not required, which is preferable.

Examples of bases which may be used as processing agents include, butare not limited to, alkali metal hydroxides, such as sodium hydroxide,potassium hydroxide, and lithium hydroxide; alkaline-earth metalhydroxides, such as calcium hydroxide, magnesium hydroxide, bariumhydroxide, and cesium hydroxide; transition metal hydroxides, such asaluminum hydroxide and zinc hydroxide; alkali metal alcoholates, such assodium methylate, sodium ethylate, sodium phenylate, lithium ethylate,and lithium butylate; alkaline-earth metal alcoholates, such asmagnesium methylate and magnesium ethylate; metal hydrides, such assodium hydride, lithium hydride, calcium hydride, lithium aluminumhydride, and aluminum borohydride; and organometallic reagents, such ashydrosulfite, n-butyllithium, tert-butyllithium, ethylmagnesium bromide,and phenylmagnesium bromide. Furthermore, alkali metals, such asmetallic lithium, metallic sodium, and metallic potassium; andalkaline-earth metals, such as metallic magnesium and metallic calciummay also be used. These bases may be used alone or in combination. Amongthem, in view of availability, cost, and reactivity, preferred aresodium hydroxide, potassium hydroxide, lithium hydroxide, calciumhydroxide, magnesium hydroxide, sodium methylate, sodium ethylate,sodium hydride, lithium hydride, metallic lithium, metallic sodium, andmetallic potassium. Because of ease of handling, more preferred aresodium hydroxide, potassium hydroxide, lithium hydroxide, calciumhydroxide, magnesium hydroxide, sodium methylate, and sodium ethylate.

Examples of acids which may be used as processing agents include, butare not limited to, inorganic acids, such as hydrochloric acid, nitricacid, sulfuric acid, phosphoric acid, hydrofluoric acid, hydrobromicacid, fluoroboric acid, chlorosulfonic acid, hydriodic acid, arsenicacid, and silicofluoric acid; organic acids, such as p-toluenesulfonicacid, trifluoromethyl sulfonic acid, acetic acid, trifluoroacetic acid,methylphosphoric acid, ethylphosphoric acid, n-propylphosphoric acid,isopropylphosphoric acid, n-butylphosphoric acid, laurylphosphoric acid,stearylphosphoric acid, 2-ethylhexylphosphoric acid, isodecylphosphoricacid, dimethyldithiophosphoric acid, diethyldithiophosphoric acid,diisopropyldithiophosphoric acid, and phenylphosphonic acid; and strongacidic ion exchange resins and weak acidic ion exchange resins.Furthermore, compounds which show acidity in reaction with a smallamount of water may also be used. Examples of such compounds includeacid anhydrides, such as acetic anhydride, propionic anhydride,trifluoroacetic anhydride, phthalic anhydride, and succinic anhydride;acyl halides; and metal halides, such as titanium tetrachloride,aluminum chloride, and silicon chloride. These acids may be used aloneor in combination. Among them, in view of availability, cost, andreactivity, preferred are hydrochloric acid, nitric acid, sulfuric acid,phosphoric acid, aluminum chloride, titanium tetrachloride,chlorosulfonic acid, p-toluenesulfonic acid, trifluoromethyl sulfonicacid, acetic acid, and trifluoroacetic acid.

Examples of hydrogen-nitrogen bond-containing compounds which may beused as processing agents include, but are not limited to, ammonia,hydrazine, primary amine compounds, secondary amine compounds, amidecompounds, amine hydrochlorides, hydrogen-nitrogen bond-containingpolymers, and hindered amine light stabilizers (HALSs).

Among the hydrogen-nitrogen bond-containing compounds, specific examplesof primary amine compounds include, but are not limited to,N-(2-aminoethyl)ethanolamine, 12-aminododecanoic acid,3-amino-1-propanol, allylamine, isopropylamine,3,3′-iminobis(propylamine), monoethylamine, 2-ethylhexylamine,3-(2-ethylhexyloxy)propylamine, 3-ethoxypropylamine,3-(diethylamino)propylamine, 3-(dibutylamino)propylamine, n-butylamine,tert-butylamine, sec-butylamine, n-propylamine,3-(methylamino)propylamine, 3-(dimethylamino)propylamine,N-methyl-3,3′-iminobis(propylamine), 3-methoxypropylamine,2-aminoethanol, ethylenediamine, diethylenetriamine,triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine,N-carboxy-4,4′-methylenebiscyclohexylamine, 1,4-diaminobutane,1,2-diaminopropane, 1,3-diaminopropane, diaminomaleonitrile,cyclohexylamine, ATU (manufactured by Ajinomoto Co., Inc.), CTUGuanamine (manufactured by Ajinomoto Co., Inc.), thiourea dioxide,2-hydroxyethylaminopropylamine, hexamethylenediamine, n-hexylamine,monomethylamine, monomethylhydrazine, 3-(lauryloxy)propylamine,anisidine, aniline, p-aminoacetanilide, p-aminobenzoic acid, ethylp-aminobenzoate ester, 2-amino-4-chlorophenol, 2-aminothiazole,2-aminothiophenol, 2-amino-5-nitrobenzonitrile, aminophenol,p-aminobenzaldehyde, 4-aminobenzonitrile, anthranilic acid,3-isopropoxyaniline, 4-amino-5-hydroxy-2,7-naphthalenesulfonic acidmonosodium salt, 6-amino-4-hydroxy-2-naphthalenesulfonic acid, xylidine,m-xylylenediamine, p-cresidine, dianisidine,4,4′-diaminostilbene-2,2′-disulfonic acid, 2-amino-5-naphthol-7-sulfonicacid, 1,4-diaminoanthraquinone,4,4′-diamino-3,3′-diethyldiphenylmethane, 4,4′-diaminobenzanilide,diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminodiphenylmethane,sulfanilic acid, tobias acid, 2,4,5-trichloroaniline, o-tolidine,toluidine, toluylenediamine, sodium naphthionate, nitroaniline,m-nitro-p-toluidine, o-chloro-p-toluidine-m-sulfonic acid,phenylhydrazine, phenylenediamine, phenetidine, phenethylamine,benzylamine, benzophenone hydrazine, mesidine, metanilic acid,2-methyl-4-nitroaniline, leuco-1,4-diaminoanthraquinone, paramine,aminopyridine, 1-(2-aminoethyl)piperazine, N-(3-aminopropyl)morpholine,1-amino-4-methylpiperazine, bis(aminopropyl)piperazine, benzoguanamine,melamine, o-chloroaniline, 2,5-dichloroaniline, 3,4-dichloroaniline,3,5-dichloroaniline, 2-amino-4-chlorobenzoic acid,o-chloro-p-nitroaniline, 5-chloro-2-nitroaniline,2,6-dichloro-4-nitroaniline, 2-(2-chlorophenyl)ethylamine,3,3¹-dichloro-4,4′-diaminodiphenylmethane,3,3′-dichloro-4,4′-diaminobiphenyl, 2,4-difluoroaniline,o-fluoroaniline, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane,N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, andγ-aminopropyltriethoxysilane.

Among the hydrogen-nitrogen bond-containing compounds, specific examplesof secondary amine compounds include, but are not limited to,N-methylethanolamine, diallylamine, diisopropylamine, diethylamine,diisobutylamine, di-2-ethylhexylamine, iminodiacetic acid,3,3′-iminodipropionitrile, bis(hydroxyethyl)amine,N-ethylethylenediamine, ethyleneimine, dicyclohexylamine,1,1-dimethylhydrazine, di-n-butylamine, di-tert-butylamine,dimethylamine, sodium N-methylacetate, N-ethylaniline, diphenylamine,dibenzylamine, 7-anilino-4-hydroxy-2-naphthalenesulfonic acid,N-methylaniline, 2-methyl-4-methoxydiphenylamine, imidazole,2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole,2-undecylimidazole, 1,3-di(4-piperidyl)propane, 2,5-dimethylpiperazine,2,6-dimethylpiperazine, 3,5-dimethylpyrazole, 5,5′-bi-1H-tetrazole,5-phenyl-1H-tetrazole, 5-methyl-1H-tetrazole,1,2,3,4-tetrahydroquinoline, (hydroxyethyl)piperazine, pipecoline,2-(1-piperazinyl)pyrimidine, piperazine, piperidine, pyrrolidine,N-methylpiperazine, 2-methylpiperazine, and morpholine.

Among the hydrogen-nitrogen bond-containing compounds, specific examplesof amide compounds include, but are not limited to,2-acrylamido-2-methylpropanesulfonic acid, dihydrazide adipate,N-isopropylacrylamide, N-t-octylacrylamide, carbohydrazides,guanylthiourea, glycylglycine, N-[3-(dimethylamino)propyl]acrylamide,N-[3-(dimethylamino)propyl]methacrylamide,N,N′-ethylenebis(stearoamide), amide oleate, amide stearate,N,N′-methylenebis(stearoamide), N-(hydroxymethyl)stearoamide, diacetoneacrylamide, thioacetoamide, thiocarbohydrazide, thiosemicarbazide,thiourea, dihydrazide dodecanedioate, dihydrazide adipate, dihydrazidesebacate, dihydrazide isophthalate,1,6-hexamethylenebis(N,N-dimethylsemicarbazide), formamide,methacrylamide, N,N′-methylenebis(acrylamide), N-methylolacrylamide,acetanilide, acetoacet-o-anisidide, acetoacetanilide,acetoacet-m-xylidide, acetoacet-o-chloroanilide,acetoacet-2,5-dimethoxy-4-chloroanilide, acetoacetic toluidide,1,1,1′,1′-tetramethyl-4,4′-(methylenedi-p-phenylene)disemicarbazide,toluene sulfonamide, p-hydroxyphenylacetamide, phthalimide, isocyanuricacid, 3-carbamoyl-2-pyrazine carboxylic acid, imide succinate,5,5-dimethylhydantoin,1,3-bis(hydrazinocarboethyl)-5-isopropylhydantoin, hydantoin,phenylpyrazolidone, 3-methyl-5-pyrazolone,1-methylol-5,5-dimethylhydantoin, 3-(4-chlorophenyl)-1,1-dimethylurea,bromovalerylurea, 2,6-difluorobenzamide, and 2,2,2-trifluoroacetamide.

Among the hydrogen-nitrogen bond-containing compounds, specific examplesof amine hydrochlorides include, but are not limited to, acetamidinehydrochloride, 2,2′-azobis-(2-amidinopropane)dihydrochloride,monomethylamine hydrochloride, dimethylamine hydrochloride,monoethylamine hydrochloride, diethylamine hydrochloride,monopropylamine hydrochloride, dipropylamine hydrochloride,monobutylamine hydrochloride, dibutylamine hydrochloride, semicarbazidehydrochloride, guanidine hydrochloride, aminoguanidine hydrochloride,2-chloroethylamine hydrochloride, cysteamine hydrochloride, andtert-butyl hydrazine monohydrochloride.

Among the hydrogen-nitrogen bond-containing compounds, specific examplesof hydrogen-nitrogen bond-containing polymers include, but are notlimited to, POLYMENT (manufactured by Nippon Shokubai Co., Ltd.),poly(ethylene imine), amino poly(acryl amide), nylon 6, nylon 66, nylon610, nylon 612, nylon 11, nylon 12, nylon MXD6, nylon 46,polyamide-imide, polyarylamine, and polyurethane.

Among the hydrogen-nitrogen bond-containing compounds, examples of HALSsinclude, but are not limited to, Adekasutabu LA-77 (manufactured byAsahi Denka Co., Ltd.), Chimassorb 944LD (manufactured by Ciba SpecialtyChemicals), Tinuvin 144 (manufactured by Ciba Specialty Chemicals),Adekasutabu LA-57 (manufactured by Asahi Denka Co., Ltd.), AdekasutabuLA-67 (manufactured by Asahi Denka Co., Ltd.), Adekasutabu LA-68(manufactured by Asahi Denka Co., Ltd.), Adekasutabu LA-87 (manufacturedby Asahi Denka Co., Ltd.), and Goodrite UV-3034 (manufactured byGoodrich Corporation).

When the thiocarbonylthio group-containing polymer is treated with theprocessing agent, the amount of the processing agent used is notparticularly limited. When an acidic compound or basic compound is usedas the processing agent, in view of ease of handling and reactivity, theamount used is preferably 0.01 to 100 parts by weight, more preferably0.05 to 50 parts by weight, and most preferably 0.1 to 30 parts byweight based on 100 parts by weight of the polymer. When the polymer istreated with an acidic compound or basic compound, in view of stabilityof the polymer, preferably, neutralization is carried out aftertreatment. When a hydrogen-nitrogen bond-containing compound is used asthe processing agent, because of a high introduction rate of mercaptogroups, the amount of the hydrogen-nitrogen bond-containing compound ispreferably 0.5 to 1,000 moles, and more preferably 1 to 500 moles, basedon 1 mole of thiocarbonylthio group in the polymer. The excesshydrogen-nitrogen bond-containing compound can be recovered and reused.It is also possible to remove the excess processing agent by passing itthrough a column packed with an adsorbent, such as silica or alumina.

Among the processing agents described above, preferred arehydrogen-nitrogen bond-containing compounds in view of no corrosion ofapparatus, the fact that neutralization is not required, and stabilityof crosslinkable silyl groups. More preferred are ammonia, primary aminecompounds with a boiling point of 100° C. or less, and secondary aminecompounds with a boiling point of 100° C. or less in view of the factthat the purification step after treatment can be simplified. Mostpreferred are ammonia, monomethylamine, dimethylamine, monoethylamine,and diethylamine in view of availability.

In the present invention, when the thiocarbonylthio group-containingvinyl polymer is treated with the processing agent, the reactionconditions are not particularly limited. For example, a method in whichthe polymer is dissolved in an organic solvent, and the processing agentis added thereto; a method in which the processing agent is added to awater-based dispersion or emulsion; or a method in which the processingagent is directly added to the solid or molten polymer itself may beemployed. The treatment temperature is not particularly limited. In viewof reactivity, the treatment temperature is preferably −50° C. to 300°C., and more preferably −10° C. to 200° C.

By using the processing agent, the block copolymers of the presentinvention, which have mercapto groups or mercaptide groups, areobtained.

The block copolymers having mercapto groups or mercaptide groups at endsare formed by treatment with the processing agent. If necessary, theblock copolymers thus obtained are subjected to a coupling reaction toproduce a block copolymer of the desired type. For example, A-B diblockcopolymers, each including a polymer block A and a polymer block Blinked to the block A, are prepared, and by coupling the A-B diblockcopolymers, block copolymers, such as A-B-A block copolymers and (A-B)nblock copolymers, are prepared.

Examples of coupling methods used for coupling the block copolymershaving mercapto groups or mercaptide groups include, but are not limitedto, methods (i) to (xi) for block copolymers having mercapto groups, andmethods (xii) to (xv) for block copolymers having mercaptide groups.Examples of coupling methods for block copolymers having mercapto groupsinclude (i) a method in which disulfide bonds are formed between blockcopolymers in the presence of an oxidizing agent, such as oxygen, leaddioxide, or calcium dioxide, and thereby the block copolymers arecoupled; (ii) a method in which a compound having at least twoisocyanato groups in each molecule is allowed to react with blockcopolymers, and thereby the block copolymers are coupled viathiourethane bonds (—NHCOS—); (iii) a method in which a compound havingat least two isothiocyanato groups in each molecule is allowed to reactwith block copolymers, and thereby the block copolymers are coupled viadithiourethane bonds (—NHCSS—); (iv) a method in which a compound havingat least two unsaturated bonds in each molecule is added to blockcopolymers, and thereby the block copolymers are coupled; (v) a methodin which dehydrocondensation is performed between a polyvalentcarboxylic acid and block copolymers, and thereby the block copolymersare coupled via thioester bonds; (vi) a method in whichtransesterification is performed between a polyvalent carboxylate esterand block copolymers, and thereby the block copolymers are coupled viathioester bonds; (vii) a method in which esterification is performedbetween a polyvalent carboxylic anhydride and block copolymers, andthereby the block copolymers are coupled via thioester bonds; (viii) amethod in which acylation is performed between a polyvalent acyl halideand block copolymers, and thereby the block copolymers are coupled viathioester bonds; (ix) a method in which block copolymers are coupled bytransesterification between a carbonate compound and the blockcopolymers; (x) a method in which a ketone is allowed to react withblock copolymers to form thioketal bonds, and thereby the blockcopolymers are coupled; and (xi) a method in which block copolymers arecoupled by dehydrocondensation between a compound having at least twohydroxyl groups in each molecule and the block copolymers. Examples ofcoupling methods for block copolymers having mercaptide groups include(xii) a method in which a compound having at least two halogen atoms ineach molecule is allowed to react with block copolymers to form sulfidebonds (Williamson reaction), and thereby the block copolymers arecoupled; (xiii) a method in which block copolymers are coupled byneutralization between a polyvalent carboxylic acid and the blockcopolymers; (xiv) a method in which block copolymers are coupled by areaction between a polyvalent carboxylic acid halide and the blockcopolymers; and (xv) a method in which disulfide bonds are formedbetween block copolymers in the presence of an oxidizing agent, andthereby the block copolymers are coupled.

In addition, it is also possible to use compounds having differentfunctional groups in each molecule. Examples of such compounds include,but are not limited to, ketones having an isocyanato group in eachmolecule, compounds having an isocyanato group and an alkenyl group ineach molecule, compounds having an isocyanato group and a halogen atomin each molecule, compounds having a hydroxyl group and a mercapto groupin each molecule, compounds having an aromatic isocyanato group and analiphatic isocyanato group in each molecule, compounds having a carboxylgroup and a halogen atom in each molecule, compounds having a hydroxylgroup and a halogen atom in each molecule, compounds having a mercaptogroup and a halogen atom in each molecule, compounds having a halogenatom and an alkenyl group in each molecule, compounds having an alkenylgroup and a mercapto group in each molecule, and compounds having anisocyanato group and an ethinyl group in each molecule.

Among these methods, in view of ease of reaction and couplingefficiency, methods (i), (iii), (xii), and (xv) are preferred.

Among the coupling methods for block copolymers having mercapto groups,when method (i), in which disulfide bonds are formed between blockcopolymers in the presence of an oxidizing agent, is employed, examplesof oxidizing agents which may be used include, but are not limited to,chlorates, such as sodium chlorate, potassium chlorate, ammoniumchlorate, barium chlorate, and calcium chlorate; perchlorates, such assodium perchlorate, potassium perchlorate, and ammonium perchlorate;inorganic peroxides, such as lithium peroxide, sodium peroxide,potassium peroxide, rubidium peroxide, cesium peroxide, magnesiumperoxide, calcium peroxide, strontium peroxide, and barium peroxide;chlorites, such as sodium chlorite, potassium chlorite, copper chlorite,and lead chlorite; bromates, such as sodium bromate, potassium bromate,magnesium bromate, and barium bromate; nitrates, such as sodium nitrate,potassium nitrate, ammonium nitrate, barium nitrate, and silver nitrate;iodates, such as sodium iodate, potassium iodate, calcium iodate, andzinc iodate; permanganates, such as potassium permanganate, sodiumpermanganate, and ammonium permanganate; bichromates, such as sodiumbichromate, potassium bichromate, and ammonium bichromate; periodates,such as sodium periodate; periodic acids, such as metaperiodic acid;chromium oxides, such as chromic anhydride (chromium trioxide); leadoxides, such as lead dioxide; iodine oxides, such as diiodine pentoxide;nitrites, such as sodium nitrite and potassium nitrite; hypochlorites,such as calcium hypochlorite; chloroisocyanuric acids, such astrichloroisocyanuric acid; peroxodisulfates, such as ammoniumperoxodisulfate; peroxoborates, such as ammonium peroxoborate;perchloric acid; hydrogen peroxide; nitric acid; halides, such aschlorine fluoride, bromine trifluoride, bromine pentafluoride, andiodine pentafluoride; iodine; and oxygen. These may be used alone or incombination as long as no danger is involved. It is also possible to usea compound which generates hydrogen peroxide in reaction with water ormoisture in air, such as calcium dioxide. Among them, because of ease ofreaction and high efficiency, preferred are sodium chlorate, sodiumperchlorate, sodium peroxide, sodium chlorite, lead dioxide, hydrogenperoxide, calcium dioxide, and oxygen.

When method (ii), in which a compound having at least two isocyanatogroups in each molecule is allowed to react with block copolymers, andthereby coupling of the block copolymers is performed via thiourethanebonds (—NHCOS—), is employed, examples of the compound having at leasttwo isocyanato groups in each molecule which may be used include, butare not limited to, diisocyanate compounds, such as hexamethylenediisocyanate, 2,4-tolylene diisocyanate, diphenylmethane diisocyanate,isophorone diisocyanate, xylylene diisocyanate,methylenebis(cyclohexylisocyanate), bis(isocyanatemethyl)cyclohexane,1,5-naphthylene diisocyanate, ethylene diisocyanate, methylenediisocyanate, propylene diisocyanate, and tetramethylene diisocyanate;triisocyanate compounds, such as 1,6,11-undecane triisocyanate andtriphenylmethane triisocyanate; polyvalent isocyanate compounds formedby reaction of these compounds with polyhydric alcohols;isocyanurate-modifications of these compounds; and polyvalent isocyanatecompounds formed by reaction of these compounds with polyvalent aminecompounds. These may be used alone or in combination. Among them, inview of availability and reactivity, preferred are hexamethylenediisocyanate, 2,4-tolylene diisocyanate, diphenylmethane diisocyanate,isophorone diisocyanate, xylylene diisocyanate,methylenebis(cyclohexylisocyanate), andbis(isocyanatemethyl)cyclohexane.

In the reaction described above, a catalyst (urethane formationcatalyst) may be used as necessary. For example, the catalysts cited inPolyurethanes: Chemistry and Technology, Part I, Table 30, Chapter 4,Saunders and Frisch, Interscience Publishers, New York, 1963 may beused, but usable catalysts are not limited thereto. As the urethaneformation reaction catalysts which may be used in the reaction describedabove, the following catalysts are preferred because of their highactivity: tin catalysts, such as tin octylate, tin stearate, dibutyltindioctoate, dibutyltin dioleylmaleate, dibutyltin dibutylmaleate,dibutyltin dilaurate,1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyldistannoxane,dibutyltindiacetate, dibutyltin diacetylacetonate, dibutyltinbis(o-phenylphenoxide), dibutyltin oxide, dibutyltinbis(triethoxysilicate), dibutyltin distearate, dibutyltinbis(isononyl-3-mercaptopropionate), dibutyltin bis(isooctylthioglycolate), dioctyltin oxide, dioctyltin dilaurate, dioctyltindiacetate, and dioctyltin diversatate; and tertiary amine compounds andtheir analogues, such as triethylamine, triphenylamine, trimethylamine,N,N-dimethylaniline, and pyridine.

The amount of the catalyst added in the reaction is not particularlylimited, but is preferably 0.0001 to 3 parts by weight, more preferably0.001 to 0.5 parts by weight, and most preferably 0.003 to 0.1 parts byweight, based on 100 parts by weight of the block copolymer havingmercapto groups or mercaptide groups. If the amount is less than 0.0001parts by weight, sufficient reactivity may not be obtained. If theamount exceeds 3 parts by weight, the properties of the resultant blockcopolymer, such as heat resistance, weatherability, and hydrolysisresistance, may be degraded.

In method (iii) in which a compound having at least two isothiocyanatogroups in each molecule is allowed to react with block copolymers, andthereby the block copolymers are coupled via dithiourethane bonds(—NHCSS—), the compound having at least two isothiocyanato groups ineach molecule used is not particularly limited. Examples thereof includecompounds obtained by replacing the isocyanato groups of the compoundhaving at least two isocyanato groups in each molecule described abovewith isothiocyanato groups.

In method (iv) in which a compound having at least two unsaturated bondsin each molecule is added to block copolymers, and thereby the blockcopolymers coupled, examples of compounds having at least twounsaturated bonds in each molecule which may be used include, but arenot limited to, butadiene, isoprene, chloroprene, 1,4-heptadiene,1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, divinyl ether, diallylether, vinyl acrylate, vinyl methacrylate, allyl acrylate, allylmethacrylate, 1,2-divinylbenzene, 1,4-divinylbenzene,1,3,5-trivinylbenzene, bisphenol A divinyl ether, bisphenol A diallylether, trimethylolpropane divinyl ether, trimethylolpropane trivinylether, trimethylolpropane diallyl ether, trimethylolpropane triallylether, acrylate of alkyl-modified dipentaerythritol, ethyleneoxide-modified bisphenol A diacrylate, acrylate ofε-caprolactone-modified dipentaerythritol, diacrylate ofcaprolactone-modified neopentyl glycol hydroxypivalate,ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate,dipentaerythritol pentaacrylate, tetraethylene glycol diacrylate,tripropylene glycol diacrylate, trimethylolpropane ethyleneoxide-modified triacrylate, trimethylolpropane triacrylate, neopentylglycol diacrylate, diacrylate of neopentyl glycol hydroxypivalate,1,9-nonanediol diacrylate, 1,4-butanediol diacrylate, 2-propenoic acid[2-[1,1-dimethyl-2-[(1-oxo-2-propenyl)oxy]ethyl]-5-ethyl-1,3-dioxane-5-yl]methylester, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, ethyleneglycol dimethacrylate, tetraethylene glycol dimethacrylate, triethyleneglycol dimethacrylate, 1,3-butylene glycol dimethacrylate,trimethylolpropane trimethacrylate, pentaerythritol divinyl ether,pentaerythritol trivinyl ether, pentaerythritol diallyl ether,pentaerythritol triallyl ether, 1,4-butanediol divinyl ether,1,4-butanediol diallyl ether, 1,5-pentanediol divinyl ether,1,5-pentanediol diallyl ether, 1,6-hexanediol divinyl ether,1,6-hexanediol diallyl ether, diethylene glycol divinyl ether,diethylene glycol diallyl ether, tripropylene glycol divinyl ether,tripropylene glycol diallyl ether, tetraethylene glycol divinyl ether,tetraethylene glycol diallyl ether, poly(ethylene oxide) divinyl ether,poly(ethylene oxide) diallyl ether, poly(propylene oxide) divinyl ether,poly(propylene oxide) diallyl ether, neopentyl glycol divinyl ether,neopentyl glycol diallyl ether, divinyl trimellitate, trivinyltrimellitate, diallyl trimellitate, triallyl trimellitate, divinylsuccinate, diallyl succinate, divinyl phthalate, diallyl phthalate,divinyl maleate, diallyl maleate, divinyl terephthalate, diallylterephthalate, divinyl carbonate, diallyl carbonate,1,3,5-triacryloylhexahydro-1,3,5-triazine, triallyl isocyanurate,triallyl cyanurate, trimethallyl isocyanurate, furan, cyclopentadiene,dicyclopentadiene, and a maleimide compound represented by generalformula (5):

(wherein R⁵ is a divalent organic group of 1 or more carbon atoms). Inview of availability, preferably, R⁵ has 1 to 20 carbon atoms. Thesecompounds may be used alone or in combination.

In method (v) in which dehydrocondensation is performed between apolyvalent carboxylic acid and block copolymers, and thereby the blockcopolymers are coupled via thioester bonds, examples of polyvalentcarboxylic acids which may be used include, but are not limited to,adipic acid, itaconic acid, iminodiacetic acid,ethylenediaminetetraacetic acid, glutaric acid, citraconic acid, oxalicacid, tartaric acid, diparatoluoyltartaric acid, dibenzoyltartaric acid,sebacic acid, 3,3′-thiodipropionic acid, thiomaleic acid, dodecanedioicacid, 1,2-cyclohexanediaminetetraacetic acid, brassylic acid, malonicacid, phthalic acid, isophthalic acid, terephthalic acid,naphthalenedicarboxylic acid, 5-hydroxyisophthalic acid,1-cyanoethyl-2-methylimidazole trimellitate,1-cyanoethyl-2-phenylimidazole trimellitate,1-cyanoethyl-2-ethyl-4-methylimidazole trimellitate,1-cyanoethyl-2-undecylimidazole trimellitate, imidazole-4,5-dicarboxylicacid, chelidamic acid, 2,3-pyrazinedicarboxylic acid, folic acid, citricacid, succinic acid, fumaric acid, malic acid, glutamic acid, asparticacid, cystine, chlorendic acid, and trimellitic acid. These may be usedalone or in combination. When block copolymers are allowed to react withthese polyvalent carboxylic acids, any esterification catalyst commonlyused may be used. By removing water produced during reaction, thereaction can be carried out effectively. For example, a method in whichthe resultant water is removed with a dehydrator, such as molecularsieves, a method in which the resultant water is removed by reactionwith an orthocarboxylate ester or the like, or a method in which theresultant water is removed with an azeotropic solvent, such as toluene,is appropriately employed.

In method (vi) in which transesterification is performed between apolyvalent carboxylate ester and block copolymers, and thereby the blockcopolymers are coupled, as the polyvalent carboxylate ester, esters ofthe polyvalent carboxylic acids described above may be used. Examples ofcarboxylate esters include, but are not limited to, methyl esters, ethylesters, n-propyl esters, isopropyl esters, n-butyl esters, isobutylesters, sec-butyl esters, tert-butyl esters, decyl esters, isodecylesters, lauryl esters, vinyl esters, allyl esters, phenyl esters, benzylesters, naphthyl esters, (4-hydroxyphenyl)esters,(4-methoxyphenyl)esters, and (4-vinylphenyl)esters. These esters may beused alone or in combination. When block copolymers are allowed to reactwith the polyvalent carboxylate esters, any transesterification catalystcommonly used may be used. In order to carry out the reactionefficiently, by-product alcohol is preferably removed by distillationunder normal or reduced pressure.

In method (vii) in which esterification is performed between apolyvalent carboxylic anhydride and block copolymers, and thereby theblock copolymers are coupled, as the polyvalent carboxylic anhydride,anhydrides of the polyvalent carboxylic acids described above may beused, but the anhydride which may be used is not limited thereto. Thesepolyvalent carboxylic anhydrides may be used alone or in combination. Inthe reaction, any transesterification catalyst commonly used may beused. In this method, by removing water produced during reaction, thereaction can also be carried out effectively. As in the case describedabove, a method in which the resultant water is removed with adehydrator, such as molecular sieves, a method in which the resultantwater is removed by reaction with an orthocarboxylate ester or the like,or a method in which the resultant water is removed with an azeotropicsolvent, such as toluene, is appropriately employed.

In method (viii) in which dehydrohalogenation (acylation) is performedbetween a polyvalent carboxylic acid halide and block copolymers, andthereby the block copolymers are coupled, as the polyvalent acyl halide,halides of the polyvalent carboxylic acids described above may be used.Specific examples of polyvalent acyl halides include, but are notlimited to, chlorinated compounds, such as succinyl dichloride, adypinyldichloride, itaconyl dichloride, oxalyl dichloride, tartaryl dichloride,malonyl dichloride, phthalyl dichloride, isophthalyl dichloride,terephthalyl dichloride, fumaryl dichloride, maleyl dichloride;compounds formed by replacing the chlorine atoms in the above-mentionedchlorinated compounds by bromine atoms; and compounds formed byreplacing the chlorine atoms in the above-mentioned chlorinatedcompounds by iodine atoms. Among them, in view of availability andreactivity, preferred are chlorinated compounds, such as succinyldichloride, malonyl dichloride, and fumaryl dichloride. These may beused alone or in combination. After the reaction, preferably, acidspresent in the system are removed by neutralization or distillationunder reduced pressure. If the acids are not removed, corrosion mayoccur.

In method (ix) in which block copolymers are coupled bytransesterification between a carbonate compound and the blockcopolymers, examples of carbonate compounds which may be used include,but are not limited to, dimethyl carbonate, diethyl carbonate,di-n-propyl carbonate, diisopropyl carbonate, di-n-butyl carbonate,diisobutyl carbonate, di-sec-butyl carbonate, di-tert-butyl carbonate,divinyl carbonate, diallyl carbonate, diphenyl carbonate, ethylenecarbonate, and propylene carbonate. These may be used alone or incombination. In the reaction between block copolymers and the carbonatecompounds, any transesterification catalyst commonly used may be used.In order to carry out the reaction efficiently, by-product alcohol ispreferably removed by distillation under normal or reduced pressure.

In method (x) in which a ketone is allowed to react with blockcopolymers to form thioketal bonds, and thereby the block copolymers arecoupled, examples of ketones which may be used include, but are notlimited to, acetylacetone, acetone, isophorone, diisobutyl ketone,diisopropyl ketone, cyclohexanone, cyclopentanone, 1,3-dihydroxyacetone,1,3-dihydroxyacetone dimethyl ether, 4,4-dimethoxy-2-butanone, diacetoneacrylamide, diacetone alcohol, 4-hydroxy-2-butanone, methyl isobutylketone, methyl isopropyl ketone, methyl ethyl ketone,methylcyclohexanone, 3-methylpentenone, anthraquinone, chloranil,1,4-diaminoanthraquinone, 1,4-dihydroxyanthraquinone,4,4′-dimethoxybenzophenone, 2,3,4-trihydroxybenzophenone,1,4-naphthoquinone, quinone, propiophenone, benzil, o-benzoylbenzoicacid, methyl o-benzoylbenzoate, benzoin, benzoin isopropyl ether,benzoin isobutyl ether, benzoin ethyl ether, benzophenone,3,3′,4,4′-benzophenonetetracarboxylic dianhydride, kojic acid, diketene,methyl 4-chloroacetoacetate, chloroacetophenone,2,3-dichloro-5,6-dicyano-1,4-benzoquinone,2,3-dichloro-1,4-naphthoquinone, and hexafluoroacetone. These may beused alone or in combination. In view of reactivity, the reaction ispreferably carried out in acidic conditions. The acid used for creatingthe acidic conditions is not particularly limited and any acid commonlyused may be used. In view of stability and corrosion resistance of theproduct, the acid is preferably neutralized after the reaction.

In method (xi) in which block copolymers are coupled bydehydrocondensation between a compound having at least two hydroxylgroups in each molecule and the block copolymers, examples of compoundshaving at least two hydroxyl groups in each molecule which may be usedinclude, but are not limited to, 3,6-dimethyl-4-octyne-3,6-diol,2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5-dimethyl-3-hexyne-2,5-diol,2,5-dimethyl-2,5-hexanediol, isoprene glycol, diisopropanolamine,triisopropanolamine, diethanolamine, triethanolamine, ethylene glycol,diethylene glycol, triethylene glycol, 2-ethyl-1,3-hexanediol, sodiumgluconate, glycerol α-monochlorohydrin, 1,4-cyclohexanediol,1,3-dihydroxyacetone, 1,4-dihydroxy-1,4-butanedisulfonic acid disodiumsalt, tartaric acid, diisopropyl tartrate, 1-thioglycerol, thiodiglycol,trimethylolethane, trimethylolpropane, trimethylolpropane monoallylether, neopentyl glycol, 1,3-butanediol, 1,4-butanediol,2-butyl-2-ethyl-1,3-propanediol, propylene glycol, dipropylene glycol,tripropylene glycol, 1,6-hexanediol, 1,2,6-hexanetriol, hexylene glycol,pentaerythritol, 1,5-pentanediol, polyethylene glycol,polytetramethylene ether glycol, polypropylene glycol,3-methyl-1,5-pentanediol, catechol, 1,4-dihydroxyanthraquinone,1,4-dihydroxynaphthalene, 2,3,4-trihydroxybenzophenone,2,3,5-trimethylhydroquinone, hydroquinone,bis(2-hydroxyethyl)terephthalate, bis(4-hydroxyphenyl)sulfone, bisphenolA, p-hydroxyphenethyl alcohol, 4-tert-butylcatechol,2-tert-butylhydroquinone, protocatechuic acid, phloroglucinol, laurylgallate, resorcin, leuco-1,4-dihydroxyanthraquinone, 1,1′-bi-2-naphthol,kojic acid, and citrazinic acid. These may be used alone or incombination. When block copolymers are allowed to react with thecompound having at least two hydroxyl groups in each molecule, anyesterification catalyst commonly used may be used. In this method, byremoving water produced during reaction, the reaction can be alsocarried out effectively. As in the case described above, a method inwhich the resultant water is removed with a dehydrator, such asmolecular sieves, a method in which the resultant water is removed byreaction with an orthocarboxylate ester or the like, or a method inwhich the resultant water is removed with an azeotropic solvent, such astoluene, is appropriately employed.

Among the coupling methods for coupling block copolymers havingmercaptide groups, in method (xii) in which a compound having at leasttwo halogen atoms in each molecule is allowed to react with blockcopolymers to form sulfide bonds (Williamson reaction), and thereby theblock copolymers are coupled, examples of compounds having at least twohalogen atoms in each molecule which may be used include, but are notlimited to, methylene chloride, 1,1,1-trichloroethane,1,2-dichloroethane, chloroform, trichloroethylene, tetrachloroethylene,2,5-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline,2,4-dichlorobenzoic acid, 2,3-dichlorotoluene, 2,4-dichlorotoluene,2,6-dichlorotoluene, 3,4-dichlorotoluene, 2,6-dichloro-4-nitroaniline,1,4-dichloro-2-nitrobenzene, 2,4-dichloro-1-nitrobenzene, o-chlorobenzylchloride, p-chlorobenzyl chloride, 2,6-dichlorobenzyl chloride,3,4-dichlorobenzyl chloride, 2,3-dichlorobenzaldehyde,2,4-dichlorobenzaldehyde, 2,6-dichlorobenzaldehyde, o-dichlorobenzene,m-dichlorobenzene, p-dichlorobenzene, 1,3,5-trichlorobenzene,2,3-dichlorobenzoyl chloride, 2,4-dichlorobenzoyl chloride,2,6-dichlorobenzoyl chloride, carbon tetrachloride,3,3′-dichloro-4,4′-diaminodiphenylmethane,3,3′-dichloro-4,4′-diaminobiphenyl,2,3-dichloro-5,6-dicyano-1,4-benzoquinone,2,3-dichloro-1,4-naphthoquinone, 2,6-dichlorobenzal chloride,2,6-dichlorobenzonitrile, octabromodiphenyl ether,1,1,2,2-tetrabromoethane, 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane,1,4-dibromobutane, 1,3-dibromopropane, 2,3-dibromo-1-propanol,1,5-dibromopentane, decabromodiphenyl ether,tetradecabromo-p-diphenoxybenzene, tetrabromocyclooctane, tetramethylenechlorobromide,2-(2-hydroxyethoxy)ethyl-2-hydroxypropyltetrabromophthalate,1-bromo-2-chloroethane, 1-bromo-3-chloropropane, 1-bromo-6-chlorohexane,bromochloromethane, hexabromobenzene, pentamethylene chlorobromide,methylene dibromide, dichloropentafluoropropane, 2,4-difluoroaniline,2,6-difluorobenzonitrile, 2,6-difluorobenzamide,2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroacetamide,trifluoroacetaldehyde hydrate, trifluoroethanol, trifluoroacetic acid,trifluoroacetic anhydride, trifluoroacetic acid ethyl ester,trifluoromethanesulfonic acid, trifluoromethanesulfonic acid anhydride,lithium trifluoromethanesulfonate, 2-(trifluoromethyl)benzaldehyde,4-(trifluoromethyl)benzaldehyde, 2-(trifluoromethyl)benzoyl chloride,perfluorooctyl iodide, 2-perfluoroalkylethanol, perfluoroalkylethylacrylate, perfluoropropyl vinyl ether, perfluoropolyalkenyl vinyl ether,1,3-bis(trifluoromethyl)benzene, 1,4-bis(trifluoromethyl)benzene,2,2-bis(4-hydroxyphenyl)hexafluoropropane, vinylidene fluoride,hexafluoroacetone trihydrate, hexafluoro-2-propanol,hexafluoropropylene, hexafluoropropylene oxide, 1,2-diiodoethane, and1,4-diiodobenzene. These may be used alone or in combination. Whentransparency is required, produced salts are preferably removed byfiltration or water washing.

In method (xiii) in which block copolymers are coupled by a reactionbetween a polyvalent carboxylic acid and the block copolymers, as thepolyvalent carboxylic acid, the same polyvalent carboxylic acids asthose used in method (v) may be used. The usable polyvalent carboxylicacids are not limited thereto. These may be used alone or incombination. in view of the durability of the resultant polymer,by-produced bases are preferably neutralized during or after thereaction.

In method (xiv) in which block copolymers are coupled by a reactionbetween a polyvalent acyl halide and the block copolymers, as thepolyvalent acyl halide, the same compounds as those used in method(viii) may be used.

In method (xv) in which disulfide bonds are formed between blockcopolymers, and thereby the block copolymers are coupled, as theoxidizing agent, the same compounds as those used in method (i) may beused.

When the block copolymers are coupled via the mercapto groups ormercaptide groups, it is also possible to use a compound having thegroups contained in the compounds described above. For example,compounds having carboxyl groups (method (v) and method (xiii)) andhydroxyl groups (method (xi)), such as salicylic acid and lactic acid;and compounds having halogen atoms (method (xii)) and carboxyl groups(method (v) and method (xiii), such as 4-chlorobenzoic acid may be usedto perform the coupling reactions.

In order to carry out the coupling reactions efficiently, organicsolvents may be used. Examples of organic solvents which may be used inthe present invention include, but are not limited to, hydrocarbonsolvents, such as heptane, octane, and mineral spirit; ester solvents,such as ethyl acetate, n-butyl acetate, isobutyl acetate, ethyleneglycol monomethyl ether acetate, and diethylene glycol monobutyl etheracetate; ketone solvents, such as acetone, methyl ethyl ketone, methylisobutyl ketone, diisobutyl ketone, and cyclohexanone; ether solvents,such as tetrahydrofuran, diethyl ether, di-n-butyl ether, dioxane,ethylene glycol dimethyl ether, and ethylene glycol diethyl ether; andaromatic petroleum solvents, such as toluene, xylene, Swasol 310(manufactured by Cosmo Oil Co., Ltd.), Swasol 1000 (manufactured byCosmo Oil Co., Ltd.), and Swasol 1500 (manufactured by Cosmo Oil Co.,Ltd.). These solvents may be used alone or in combination. The reactiontemperature is not particularly limited. In view of reactivity, thereaction temperature is preferably in the range of 0° C. to 200° C.

As the thermoplastic resin, which is contained in the thermoplasticresin composition of the present invention, various thermoplastic resinswhich are conventionally used may be used. Examples of thermoplasticresins include, but are not limited to, ionomer resins, such as SURLYN(manufactured by E. I. Du Pont de Nemours and Company), and HIMILAN(manufactured by Du Pont-Mitsui Polychemicals Co., Ltd.); polyacrylicacid hydrazide, isobutylene-maleic anhydride copolymers,acrylonitrile-styrene-acrylic rubber copolymers (AAS),acrylonitrile-EPDM-styrene copolymers (AES), acrylonitrile-styrenecopolymers (AS), acrylonitrile-butadiene-styrene copolymers (ABS), andABS-vinyl chloride self-extinguishing resins, such as Kaneka Enplex(manufactured by Kaneka Corporation); ABS heat-resistant resins, such asKaneka MUH (manufactured by Kaneka Corporation);acrylonitrile-chlorinated polyethylene-styrene resins (ACS), methylmethacrylate-butadiene-styrene copolymers (MBS), ethylene-vinyl chloridecopolymers, ethylene-vinyl acetate copolymers (EVA), modifiedethylene-vinyl acetate copolymers, chlorinated ethylene-vinyl acetatecopolymers, ethylene-vinyl acetate-vinyl chloride graft copolymers,ethylene-vinyl alcohol copolymers (EVOH), chlorinated poly(vinylchloride), chlorinated polyethylene, chlorinated polypropylene,carboxyvinyl polymers, ketone resins, norbornene resins,polytetrafluoroethylene (PTFE), ethylene fluoride-propylene copolymers,tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers (PFA),polychlorotrifluoroethylene, ethylene-tetrafluoroethylene copolymers,low-melting-point ethylene-tetrafluoroethylene copolymers,poly(vinylidene fluoride) (PVDF), poly(vinyl fluoride), polyacetal,polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 11,polyamide 12, copolymerized polyamides, polyamide MXD6, polyamide 46,methoxymethylated polyamides, polyamideimides, polyarylates,thermoplastic polyimides, polyether imides, polyether ether ketones,polyethylene, poly(ethylene oxide), poly(ethylene terephthalate) (PET),poly(ethylene naphthalate), poly(vinylidene chloride), poly(vinylchloride) (PVC), polycarbonate, poly(vinyl acetate), polystyrene,polysulfone, poly(ether sulfone), poly(amine sulfone),polyparavinylphenol, polyparamethylstyrene, polyallylamine, poly(vinylalcohol) (PVA), polyvinyl ether, poly(vinyl butyral) (PVB), poly(vinylformal) (PVF), polyphenylene ether, modified polyphenylene ether,poly(phenylene sulfide), polybutadiene, poly(butylene terephthalate)(PBT), polypropylene, polymethylpentene, poly(methyl methacrylate), andvarious types of liquid crystal polymers. These may be used alone or incombination. Among them, because of the excellence in heat resistance,weatherability, and oil resistance, at least one resin selected from thegroup consisting of poly(vinyl chloride), poly(methyl methacrylate),acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrenecopolymers, polycarbonate, polyester resins, and polyamide resins ispreferable.

An elastomer composition of the present invention contains the blockcopolymer and a synthetic rubber. Examples of such a synthetic rubberinclude, but are not limited to, styrene-butadiene rubber (SBR),butadiene rubber (BR), isoprene rubber (IR), ethylene-propylenecopolymer rubber (EPM), ethylene-propylene-diene copolymer rubber(EPDM), acrylonitrile-butadiene copolymer rubber (NBR), chloroprenerubber, butyl rubber (IIR), urethane rubber, silicone rubber,polysulfide rubber, hydrogenated nitrile rubber, fluororubber, ethylenetetrafluoride-propylene rubber, ethylenetetrafluoride-propylene-vinylidene fluoride rubber, acrylic rubber(ACM), chlorosufonated polyethylene rubber, epichlorohydrin rubber (CO),ethylene-acrylic rubber, norbornene rubber, styrene-based thermoplasticelastomers (SBC), olefinic thermoplastic elastomers (TPO),urethane-based thermoplastic elastomers (TPU), polyester-basedthermoplastic elastomers (TPEE), polyamide-based thermoplasticelastomers (TPAE), 1,2-polybutadiene-based thermoplastic elastomers,vinyl chloride-based thermoplastic elastomers (TPVC), andfluorine-containing thermoplastic elastomers. These may be used alone orin combination.

Each of the thermoplastic resin composition and the elastomercomposition of the present invention may contain both a thermoplasticresin and a synthetic rubber besides the block copolymer. Thecomposition may be dynamically crosslinked by a method which is commonlyused.

In the thermoplastic resin composition and elastomer composition of thepresent invention, in order to adjust various physical properties, atleast one type of additives may be compounded as necessary, besides thethermoplastic resin, the elastomer resin, and the block copolymer. Asthe additive, at least one material selected from the group consistingof plasticizers, thixotropy-improving agents, heat resistance-improvingagents, stabilizers, antioxidants, ultraviolet absorbers, hindered aminelight stabilizers (HALSs), antistatic agents, fire retardants,colorants, blowing agents, lubricants, mildewproofing agents, nucleatingadditives, vulcanization accelerators, aging resisters, vulcanizingagents, antiscorching agents, peptizers, tackifiers, latex coagulants,processing aids, inorganic fillers, and natural rubber may be used.Optimum additives may be selected depending on the types andcompositions of the thermoplastic resins and the elastomers, thecompositions of the block copolymers, the applications of thecompositions, etc.

The block copolymers of the present invention have heat resistance,weatherability, oil resistance, and flame retardancy which areoriginally exhibited by the acrylonitrile and methacrylonitrilepolymers, and furthermore are excellent in low-temperature resistance.Consequently, the block copolymers can be used in various applications,such as films, sheets, tapes, hoses, tubes, gaskets, packings, grips,various molded objects, sealants, damping materials, pressure-sensitiveadhesives, adhesives, resin modifiers, coating materials, pottingmaterials, textiles, materials for thermoplastic resin compositions, andmaterials for elastomers.

The thermoplastic resin compositions of the present invention containthe block copolymers and thermoplastic resins. The elastomercompositions of the present invention contain the block copolymers andsynthetic rubbers. These compositions can be used widely in variousapplications, such as films, sheets, tapes, hoses, tubes, gaskets,packings, grips, containers, various molded objects, sealants, dampingmaterials, pressure-sensitive adhesives, adhesives, coating materials,potting materials, and textiles.

BEST MODE FOR CARRYING OUT THE INVENTION

While the present invention will be described based on the examplesbelow, it is to be understood that the invention is not limited thereto.

In the examples below, the weight-average molecular weight (Mw),number-average molecular weight (Mn), and molecular weight distribution(Mw/Mn) were determined by gel permeation chromatography (GPC). In theGPC, chloroform, tetrahydrofuran, or dimethylformamide was used as aneluent, and a polystyrene gel column was used. The analysis was carriedout on the basis of a polystyrene standard sample.

EXAMPLE 1 Synthesis of Mercapto Group-terminated acrylonitrile-n-butylacrylate diblock copolymer

Into a 2 L reactor equipped with an agitator, a thermometer, a nitrogengas inlet tube, a dropping funnel, and a reflux condenser, was placed490 g of distilled water and 0.56 g of sodium dodecyl sulfate, and thereactor was nitrogen-purged while the reaction mixture was being stirredat 80° C. A mixed solution of 8.8 g of acrylonitrile and 1.09 g of acompound represented by formula (6):

was added into the reactor, and stirring was performed at 80° C. for 20minutes. Next, 0.93 g of 4,4′-azobis(4-cyanovaleric acid) together with25 g of distilled water was added into the reactor. Stirring wasperformed at 80° C. for 30 minutes, and then 45.0 g of acrylonitrile wasdripped from the dropping funnel for over 1 hour. After dripping wascompleted, stirring was performed at 80° C. for 5 hours, and samplingwas performed. Production of polyacrylonitrile (Mw=13,700, Mn=10,300,and Mw/Mn=1.33) was confirmed by gel permeation chromatography analysis.

Next, 20.0 g of n-butyl acrylate was added into the reactor, and 0.40 gof 4,4′-azobis(4-cyanovaleric acid) together with 10 g of distilledwater was further added thereinto. Stirring was performed at 80° C. for1 hour, and then 80.0 g of n-butyl acrylate was dripped from thedropping funnel for over 2 hours. After dripping was completed, themixture was stirred at 80° C. for 5 hours and then cooled to roomtemperature. A salting-out method was performed, followed by filtration,washing, and drying. Thereby, production of an acrylonitrile-n-butylacrylate diblock copolymer (Mw=48,600, Mn=34,500, and Mw/Mn=1.41) wasconfirmed.

The diblock copolymer (50 g) was dissolved in 200 mL of toluene, and 15g of monoethylamine was added thereinto, followed by stirring at 30° C.for 8 hours. ¹H NMR analysis and IR analysis confirmed that thethiocarbonylthio groups at ends were quantitatively converted intomercapto groups. The toluene solution was washed with water and thenpoured into methanol to precipitate and isolate the block copolymer.

EXAMPLE 2 Synthesis of Mercapto Group-terminatedMethacrylonitrile-n-butyl Acrylate Diblock Copolymer

Into a 2 L reactor equipped with an agitator, a thermometer, a nitrogengas inlet tube, a dropping funnel, and a reflux condenser, was placed490 g of distilled water and 0.55 g of sodium dodecyl sulfate, and thereactor was nitrogen-purged while the reaction mixture was being stirredat 80° C. A mixed solution of 11.3 g of methacrylonitrile and 1.08 g ofa compound represented by formula (6):

was added into the reactor, and stirring was performed at 80° C. for 20minutes. Next, 0.93 g of 4,4′-azobis(4-cyanovaleric acid) together with25 g of distilled water was added into the reactor. Stirring wasperformed at 80° C. for 30 minutes, and then 57.7 g of methacrylonitrilewas dripped from the dropping funnel for over 1 hour. After dripping wascompleted, stirring was performed at 80° C. for 5 hours, and samplingwas performed. Production of polymethacrylonitrile (Mw=16,400,Mn=13,000, and Mw/Mn=1.26) was confirmed by gel permeationchromatography analysis.

Next, 20.0 g of n-butyl acrylate was added into the reactor, and 0.36 gof 4,4′-azobis(4-cyanovaleric acid) together with 13 g of distilledwater was further added thereinto. Stirring was performed at 80° C. for1 hour, and then 80.0 g of n-butyl acrylate was dripped from thedropping funnel for over 2 hours. After dripping was completed, themixture was stirred at 80° C. for 4 hours and then cooled to roomtemperature. A salting-out method was performed, followed by filtration,washing, and drying. Thereby, production of a methacrylonitrile-n-butylacrylate diblock copolymer (Mw=49,900, Mn=36,300, and Mw/Mn=1.37) wasconfirmed.

The diblock copolymer (70 g) thus obtained was dissolved in 300 mL oftoluene, and 18 g of monoethylamine was added thereinto, followed bystirring at 30° C. for 16 hours. ¹H NMR analysis and IR confirmed thatthe thiocarbonylthio groups at ends were quantitatively converted intomercapto groups. The toluene solution was washed with water and thenpoured into methanol to precipitate and isolate the block copolymer.

EXAMPLE 3 Synthesis of Mercapto Group-terminated Acrylonitrile-(n-butylAcrylate/ethyl Acrylate) Diblock Copolymer

Into a 300 mL reactor equipped with an agitator, a thermometer, anitrogen gas inlet tube, a dropping funnel, and a reflux condenser, wasplaced 110 mg of sodium dodecyl sulfate and 100 g of distilled water,and the reactor was nitrogen-purged while the reaction mixture was beingstirred at 80° C. A compound (217 mg) represented by

which was dissolved in 1.6 g of acrylonitrile, was added into thereactor, and after 20 minutes, 185 mg of 4,4′-azobis(4-cyanovalericacid) together with 5 g of distilled water was added into the reactor.Stirring was performed at 80° C. for 20 minutes, and then 9.3 g ofacrylonitrile was dripped from the dropping funnel for over 50 minutes.After dripping was completed, stirring was performed at 80° C. for 3hours, and sampling was performed. Production of polyacrylonitrile(Mw=18,100, Mn=12,700, and Mw/Mn=1.42) was confirmed by gel permeationchromatography analysis.

Next, a mixed solution of 10.0 g of n-butyl acrylate and 7.8 g of ethylacrylate was dripped from the dropping funnel for over 1 hour. Stirringwas performed at 80° C. for 5 hours, and an emulsion was therebyprepared. Sampling was performed and production of a thiocarbonylthiogroup-terminated acrylonitrile-(n-butyl acrylate/ethyl acrylate) diblockcopolymer (Mw=48,500, Mn=31,600, and Mw/Mn=1.53) was confirmed.

Diethylamine (20 g) was added into the emulsion, and stirring wasperformed at 60° C. for 5 hours. A salting-out method was performed,followed by filtration, washing, and drying, and a polymer was therebyproduced. It was confirmed that the polymer was a mercaptogroup-terminated acrylonitrile-(n-butyl acrylate/ethyl acrylate) diblockcopolymer (Mw=48,700, Mn=31,300, and Mw/Mn=1.56).

EXAMPLE 4 Synthesis of Mercaptide Group-terminated (Acrylonitrile/MethylMethacrylate)-(n-butyl Acrylate/2-hydroxyethyl Acrylate) DiblockCopolymer)

Into a 1 L reactor equipped with an agitator, a thermometer, a nitrogengas inlet tube, a dropping funnel, and a reflux condenser, was placed200 mg of sodium dodecyl sulfate and 200 g of distilled water, and thereactor was nitrogen-purged while the reaction mixture was being stirredat 80° C. A compound (651 mg) represented by formula (6):

which was dissolved in 5.0 g of methyl methacrylate, was added into thereactor, and after 20 minutes, 500 mg of 4,4′-azobis(4-cyanovalericacid) together with 12 g of distilled water was added into the reactor.Stirring was performed at 80° C. for 30 minutes, and then a mixedsolution of 18.6 g of acrylonitrile and 6.8 g of methyl methacrylate wasdripped from the dropping funnel for over 1 hour. Stirring was thenperformed at 80° C. for 6 hours, and sampling was performed. Productionof a thiocarbonylthio group-terminated acrylonitrile/methyl methacrylaterandom copolymer was confirmed.

Next, 200 mg of 4,4′-azobis(4-cyanovaleric acid) was added into thereactor, and a mixed solution of 50.0 g of n-butyl acrylate and 18.6 gof 2-hydroxyethyl acrylate was dripped from the dropping funnel for over3 hours. Stirring was performed at 80° C. for 5 hours, and the resultantemulsion was sampled. Production of a thiocarbonylthio group-terminated(acrylonitrile/methyl methacrylate)-(n-butyl acrylate/2-hydroxyethylacrylate) diblock copolymer was confirmed. The emulsion was salted out,followed by filtration, washing, and drying, and the diblock copolymerwas thereby prepared.

The diblock copolymer (30 g) thus obtained was dissolved in 100 mL ofdehydrated toluene, and 4 g of sodium methylate was added thereinto,followed by stirring at 50° C. for 2 hours. A toluene solutioncontaining a mercaptide group-terminated (acrylonitrile/methylmethacrylate)-(n-butyl acrylate/2-hydroxyethyl acrylate) diblockcopolymer was thereby prepared. A portion of the solution was collectedas a sample and hydrolyzed, and then poured into hexane to precipitateand isolate the copolymer. ¹H NMR analysis and GPC analysis confirmedthe production of a mercapto group-terminated (acrylonitrile/methylmethacrylate)-(n-butyl acrylate/2-hydroxyethyl acrylate) diblockcopolymer (Mw=52,100, Mn=35,200, and Mw/Mn=1.48).

EXAMPLE 5 Synthesis of Acrylonitrile-n-butyl Acrylate-acrylonitrileTriblock Copolymer

Toluene (150 parts by weight) and lead dioxide (0.5 parts by weight)were added to the mercapto group-terminated acrylonitrile-n-butylacrylate diblock copolymer (100 parts by weight) synthesized in Example1, and thorough mixing was performed. The mixture was placed into a slabmold and dried in an air atmosphere at 80° C. for 15 hours. ¹H NMRanalysis, IR analysis, and gel permeation chromatography analysisconfirmed that the resultant sheet-shaped polymer was anacrylonitrile-n-butyl acrylate-acrylonitrile triblock copolymer havingdisulfide bonds in the main chain (Mw=101,600, Mn=67,300, andMw/Mn=1.51).

EXAMPLE 6 Synthesis of Acrylonitrile-n-butyl Acrylate-acrylonitrileTriblock Copolymer

Dehydrated toluene (200 parts by weight), hexamethylene diisocyanate(0.24 parts by weight), and dibutyltin bis(isooctyl thioglycolate)(0.001 parts by weight) were added to the mercapto group-terminatedacrylonitrile-n-butyl acrylate diblock copolymer (100 parts by weight)synthesized in Example 1, and stirring was performed at 80° C. for 10hours. The solvent was removed by distillation. ¹H NMR analysis, IRanalysis, and gel permeation chromatography analysis confirmed that theresultant polymer was an acrylonitrile-n-butyl acrylate-acrylonitriletriblock copolymer having thiourethane bonds in the main chain(Mw=99,700, Mn=66,500, and Mw/Mn=1.50).

EXAMPLE 7 Synthesis of Methacrylonitrile-n-butylAcrylate-methacrylonitrile Triblock Copolymer

Calcium dioxide (1 part by weight) was added to the mercaptogroup-terminated methacrylonitrile-n-butyl acrylate diblock copolymer(100 parts by weight) synthesized in Example 2, and the mixture wasroll-kneaded at 100° C. and formed into a sheet. Furthermore, the sheetwas heated at 100° C. for 5 hours and matured at room temperature for 3days. ¹H NMR analysis, IR analysis, and gel permeation chromatographyanalysis confirmed that the resultant sheet-shaped polymer was amethacrylonitrile-n-butyl acrylate-methacrylonitrile triblock copolymerhaving disulfide bonds in the main chain (Mw=102,700, Mn=71,400, andMw/Mn=1.44).

EXAMPLE 8 Synthesis of Methacrylonitrile-n-butylAcrylate-methacrylonitrile Triblock Copolymer

Dehydrated toluene (100 parts by weight), isophorone diisocyanate (0.31parts by weight), and dibutyltin bisacetylacetonate (0.001 parts byweight) were added to the mercapto group-terminatedmethacrylonitrile-n-butyl acrylate diblock copolymer (100 parts byweight) synthesized in Example 2, and the mixture was stirred at 80° C.for 8 hours. Toluene was then removed by distillation. ¹H NMR analysis,IR analysis, and gel permeation chromatography analysis confirmed thatthe resultant polymer was a methacrylonitrile-n-butylacrylate-methacrylonitrile triblock copolymer having thiourethane bondsin the main chain (Mw=98,500, Mn=69,900, and Mw/Mn=1.41).

EXAMPLE 9 Synthesis of Acrylonitrile-(n-butyl Acrylate-ethylAcrylate)-acrylonitrile Triblock Copolymer

Toluene (200 parts by weight) was added to the mercapto group-terminatedacrylonitrile-(n-butyl acrylate/ethyl acrylate) diblock copolymer (100parts by weight) synthesized in Example 3, and the mixture was stirredat 90° C. for 18 hours under blown air. Toluene was removed bydistillation. ¹H NMR analysis, IR analysis, and gel permeationchromatography analysis confirmed that the resultant polymer was anacrylonitrile-(n-butyl acrylate/ethyl acrylate)-acrylonitrile triblockcopolymer having disulfide bonds in the main chain (Mw=102,400,Mn=61,100, and Mw/Mn=1.68).

EXAMPLE 10 Synthesis of Acrylonitrile-(n-butyl Acrylate/ethylAcrylate)-acrylonitrile Triblock Copolymer

Toluene (200 parts by weight) and diphenylmethane diisocyanate (0.4parts by weight) were added to the mercapto group-terminatedacrylonitrile-(n-butyl acrylate/ethyl acrylate) diblock copolymer (100parts by weight) synthesized in Example 3, and the mixture was stirredat 100° C. for 8 hours. Toluene was removed by distillation. ¹H NMRanalysis, IR analysis, and gel permeation chromatography analysisconfirmed that the resultant polymer was an acrylonitrile-(n-butylacrylate/ethyl acrylate)-acrylonitrile triblock copolymer havingthiourethane bonds in the main chain (Mw=100,700, Mn=60,900, andMw/Mn=1.65).

EXAMPLE 11 Synthesis of (Acrylonitrile/methyl Methacrylate)-(n-butylAcrylate/2-hydroxyethyl Acrylate)-(acrylonitrile/methyl Methacrylate)Triblock Copolymer

To a toluene solution containing the (acrylonitrile/methylmethacrylate)-(n-butyl acrylate/2-hydroxyethyl acrylate) diblockcopolymer (100 parts by weight on the basis of the polymer) was added1,2-dichloroethane (0.14 parts by weight), and the mixture was stirredat 80° C. for 20 hours. The resultant toluene solution was washed withwater and dried, and the solvent was removed by distillation. ¹H NMRanalysis and GPC analysis confirmed that the resultant polymer was an(acrylonitrile/methyl methacrylate)-(n-butyl acrylate/2-hydroxyethylacrylate)-(acrylonitrile/methyl methacrylate) triblock copolymer havingsulfide bonds (Mw=101,700, Mn=65,100, and Mw/Mn=1.56).

EXAMPLE 12 Synthesis of Mercapto Group-terminated Acrylonitrile-n-butylAcrylate Diblock Copolymer

Into a 2 L reactor equipped with an agitator, a thermometer, a nitrogengas inlet tube, a dropping funnel, and a reflux condenser, was placed490 g of distilled water, 20 g of polyoxyethylene nonylphenyl ether as anonionic emulsifier, and 2 g of hexadecane as an emulsifying aid, andthe reactor was nitrogen-purged while the reaction mixture was beingstirred at 80° C. A mixed solution of 8.9 g of acrylonitrile and 1.1 gof a compound represented by formula (6):

was added into the reactor, and stirring was performed at 70° C. for 30minutes. Next, 0.92 g of 4,4′-azobis(4-cyanovaleric acid) together with25 g of distilled water was added into the reactor. Stirring wasperformed at 70° C. for 1 hour, and then 45 g of acrylonitrile wasdripped from the dropping funnel for over 1 hour. As soon as drippingwas completed, the temperature was raised to 80° C. and stirring wasperformed for 5 hours. Sampling was then performed. Production ofpolyacrylonitrile (Mw=13,000, Mn=10,000, and Mw/Mn=1.30) was confirmedby gel permeation chromatography analysis.

Next, 20 g of n-butyl acrylate was added into the reactor, and 0.25 g of4,4′-azobis(4-cyanovaleric acid) together with 5 g of distilled waterwas further added thereinto. Stirring was performed at 80° C. for 1hour, and then 80 g of n-butyl acrylate was dripped from the droppingfunnel for over 2 hours. After dripping was completed, the mixture wasstirred at 80° C. for 6 hours and then cooled to room temperature. Asalting-out method was performed, followed by filtration, washing, anddrying. Thereby, production of an acrylonitrile-n-butyl acrylate diblockcopolymer (Mw=47,500, Mn=34,000, and Mw/Mn=1.40) was confirmed.

The diblock copolymer (50 g) thus produced was dissolved in 200 mL oftoluene, and 20 g of diethylamine was added thereinto, followed bystirring at 50° C. for 8 hours. The reaction solution was purified witha silica gel column, and toluene was removed by distillation. ¹H NMRanalysis and IR analysis confirmed that the thiocarbonylthio groups atends were quantitatively converted into mercapto groups.

EXAMPLE 13 Synthesis of Acrylonitrile-n-butyl Acrylate-acrylonitrileTriblock Copolymer

Toluene (100 parts by weight), dimethylformamide (50 parts by weight),and lead dioxide (0.5 parts by weight) were added to the mercaptogroup-terminated acrylonitrile-n-butyl acrylate diblock copolymer (100parts by weight) synthesized in Example 12, and thorough mixing wasperformed. The mixture was placed into a slab mold and dried in an airatmosphere at 80° C. for 5 hours. Deaeration was performed under reducedpressure at 80° C. to remove the solvent, and heating was furtherperformed in an air atmosphere at 80° C. for 10 hours. ¹H NMR analysis,IR analysis, and gel permeation chromatography analysis confirmed thatthe resultant polymer constituting the sheet was anacrylonitrile-n-butyl acrylate-acrylonitrile triblock copolymer havingdisulfide bonds in the main chain (Mw=99,900, Mn=66,500, andMw/Mn=1.50).

PRODUCTION EXAMPLE 1 Synthesis of mercapto group-terminatedpolyacrylonitrile

Into a 2 L reactor equipped with an agitator, a thermometer, a nitrogengas inlet tube, a dropping funnel, and a reflux condenser, was placed490 g of distilled water and 0.56 g of sodium dodecyl sulfate, and thereactor was nitrogen-purged while the reaction mixture was being stirredat 80° C. A mixed solution of 8.8 g of acrylonitrile and 1.09 g of2-(2-phenylpropyl)dithiobenzoate represented by formula (6):

was added into the reactor, and stirring was performed at 80° C. for 15minutes under nitrogen flow. Next, 0.93 g of 4,4′-azobis(4-cyanovalericacid) together with 25 g of distilled water was added into the reactor.Stirring was performed at 80° C. for 1 hour, and then 45.0 g ofacrylonitrile was dripped from the dropping funnel for over 2 hours.After dripping was completed, stirring was further performed at 80° C.for 5 hours. The resultant emulsion was cooled to 30° C., and 30 g ofmonoethylamine was added thereinto, followed by stirring at 30° C. for10 hours. The emulsion was salted out, followed by filtration andwashing. Polyacrylonitrile having a mercapto group at one end wasthereby produced (Mw=13,400, Mn=10,800, and Mw/Mn=1.24).

PRODUCTION EXAMPLE 2 Synthesis of Mercapto Group-terminatedAcrylonitrile-methyl Methacrylate Random Copolymer

Into a 1 L reactor equipped with an agitator, a thermometer, a nitrogengas inlet tube, a dropping funnel, and a reflux condenser, was placed200 mg of sodium dodecyl sulfate and 200 g of distilled water, and thereactor was nitrogen-purged while the reaction mixture was being stirredat 80° C. 2-(2-Phenylpropyl)dithiobenzoate (651 mg) represented byformula (6):

was dissolved in a mixed solution of 18.6 g of acrylonitrile and 11.8 gof methyl methacrylate, and the solution was dripped from the droppingfunnel at one time. After 20 minutes, 500 mg of4,4′-azobis(4-cyanovaleric acid) together with 12 g of distilled waterwas added into the reactor. Stirring was performed at 80° C. for 4hours, and the reaction mixture was cooled to 30° C. Monoethylamine (10g) was added thereinto, and stirring was performed at 30° C. for 10hours. The resultant emulsion was salted out, followed by filtration andwashing. An acrylonitrile-methyl methacrylate random copolymer having amercapto group at one end was thereby produced (Mw=11,100, Mn=9,700, andMw/Mn=1.14).

PRODUCTION EXAMPLE 3 Synthesis of poly(n-butyl acrylate) having mercaptogroup at one end

Into a 2 L reactor equipped with an agitator, a thermometer, a nitrogengas inlet tube, a dropping funnel, and a reflux condenser, was placed0.56 g of sodium dodecyl sulfate and 490 g of distilled water, and thereactor was nitrogen-purged while the reaction mixture was being stirredat 80° C. 2-(2-Phenylpropyl)dithiobenzoate (1.09 g) represented byformula (6):

was dissolved in 16.5 g of n-butyl acrylate, and the solution wasdripped from the dropping funnel at one time. After 20 minutes, 0.93 gof 4,4′-azobis(4-cyanovaleric acid) together with 25 g of distilledwater was added into the reactor. Stirring was performed at 80° C. for30 minutes, and then 100 g of n-butyl acrylate was dripped from thedropping funnel for over 2 hours. Stirring was further performed at 80°C. for 5 hours, and the reaction mixture was cooled to 30° C.Monoethylamine (30 g) was added thereinto, and stirring was performed at30° C. for 10 hours. The resultant emulsion was salted out, followed byfiltration and washing. Poly(n-butyl acrylate) having a mercapto groupat one end was thereby produced (Mw=38,900, Mn=30,900, and Mw/Mn=1.26).

PRODUCTION EXAMPLE 4 Synthesis of poly(n-butyl acrylate) having mercaptogroups at both ends

Into a 1 L reactor equipped with an agitator, a thermometer, a nitrogengas inlet tube, and a reflux condenser tube, was placed 181 g of n-butylacrylate, 40 mg of 1,1′-azobis(1-cyclohexanecarbonitrile), 635 mg of1,4-bis(thiobenzoylthiomethyl)benzene represented by formula (7):

and 300 mL of toluene, and the reactor was nitrogen-purged. The reactionliquid was heated at 90° C. for 5 hours while being stirred. Samplingwas performed, and GPC analysis confirmed the production of a polymer(Mw=77,000, Mn=56,900, and Mw/Mn=1.35). ¹H NMR measurement confirmedthat thiocarbonylthio groups were introduced into both ends ofpoly(n-butyl acrylate), and the introduction rate was 93% on theboth-ends basis. The conversion rate of n-butyl acrylate was 55%.

Monoethylamine (30 g) was added into the resultant toluene solutioncontaining poly(n-butyl acrylate) having thiocarbonylthio groups at bothends, followed by stirring at 30° C. for 5 hours. Sampling wasperformed, and ¹H NMR measurement confirmed the production ofpoly(n-butyl acrylate) having mercapto groups at both ends. Theintroduction rate of mercapto groups was 90% on the both-ends basis.

PRODUCTION EXAMPLE 5 Synthesis of n-butyl acrylate-2-methoxyethylacrylate random copolymer

Into a 1 L reactor equipped with an agitator, a thermometer, a nitrogengas inlet tube, a reflux condenser, and a dropping funnel, was placed410 mg of sodium dodecyl sulfate and 400 g of distilled water, and thereactor was nitrogen-purged while the reaction mixture was being stirredat 80° C. A compound (23.34 g) represented by formula (8):

which was dissolved in 50 g of n-butyl acrylate, was added into thereactor, and stirring was performed at 80° C. for 20 minutes undernitrogen flow. Next, 7.0 g of 4,4′-azobis(4-cyanovaleric acid) togetherwith 25 g of distilled water was added thereinto. Stirring was performedat 80° C. for 30 minutes, and then a mixed solution of 100 g of n-butylacrylate and 50 g of 2-methoxyethyl acrylate was dripped from thedropping funnel for over 1.5 hours. After dripping was completed, themixture was stirred at 80° C. for 4 hours, and the resultant emulsionwas then cooled to room temperature. A salting-out method was performed,followed by filtration and washing. Thereby, an n-butylacrylate-2-methoxyethyl acrylate random copolymer havingthiocarbonylthio groups at both ends was produced. GPC analysis and ¹HNMR analysis confirmed that in the polymer, Mw=4,320, Mn=3,970, andMw/Mn=1.09 and that the introduction rate of thiocarbonylthio groups was97% on the both-ends basis.

The polymer having thiocarbonylthio group at both ends (180 g) wasdissolved in 200 mL of toluene, and 20 g of monoethylamine was addedthereinto, followed by stirring at 5° C. for 10 hours. By removingexcess monoethylamine and toluene, an n-butyl acrylate-2-methoxyethylacrylate random copolymer having mercapto groups at both ends wasproduced.

PRODUCTION EXAMPLE 6 Synthesis of mercapto group-terminated poly(vinylchloride)

Into a 300 L stainless steel autoclave was placed 130 kg ofion-exchanged water, 100 kg of vinyl chloride monomer, 500 g of2,2′-azobis(isobutylvaleronitrile), 400 g of sodium lauryl sulfate, and110 g of a compound represented by formula (9) below.

Homogenizing was performed for 90 minutes with a homogenizer, andpolymerization was then carried out at 50° C. When the internal pressureof the reactor became lower than the saturated vapor pressure of thevinyl chloride monomer at 50° C. by 1 kg/cm², unreacted monomers wereremoved from the reactor by distillation. A vinyl chloride polymer latexwas thereby produced. Excess vinyl chloride was removed, and the reactorwas filled with ammonia at a rate of 5 kg/cm² (20° C.). Stirring wasperformed at 50° C. for 5 hours. By spray drying the emulsion, mercaptogroup-terminated poly(vinyl chloride) was produced (Mw=61,000,Mn=41,000, and Mw/Mn=1.49).

PRODUCTION EXAMPLE 7 Synthesis of mercapto group-terminatedpolyacrylonitrile

Into a 2 L reactor equipped with an agitator, a thermometer, a nitrogengas inlet tube, a dropping funnel, and a reflux condenser, was placed490 g of distilled water, 20 g of polyethylene glycol nonylphenyl etheras a nonionic emulsifier, and 2 g of hexadecane as an emulsifying aid,and the reactor was nitrogen-purged while the reaction mixture was beingstirred at 80° C. A mixed solution of 8.9 g of acrylonitrile and 1.1 gof a compound represented by formula (6):

was added into the reactor, and stirring was performed at 70° C. for 30minutes. Next, 0.92 g of 4,4′-azobis(4-cyanovaleric acid) together with25 g of distilled water was added into the reactor. Stirring wasperformed at 70° C. for 1 hour, and then 45 g of acrylonitrile wasdripped from the dropping funnel for over 1 hour. As soon as drippingwas completed, the temperature was raised to 80° C. and stirring wasperformed for 6 hours. The mixture was cooled to room temperature, andan emulsion was prepared. The emulsion was dried and washed withacetone, and then reprecipitation was performed withdimethylformamide-acetone. Polyacrylonitrile was thereby produced. Gelpermeation chromatography analysis confirmed that Mw=13,100, Mn=9,800,and Mw/Mn=1.34.

The resultant polyacrylonitrile (30 g) was dissolved in 300 mL ofdimethylformamide, and 8 g of diethylamine was added thereinto, followedby stirring at 50° C. for 10 hours. The reaction solution wasconcentrated and reprecipitated with methanol. Mercapto group-terminatedpolyacrylonitrile was thereby produced. NMR analysis confirmed that theintroduction rate of mercapto groups was 91% on the single-end basis.

EXAMPLE 14 Synthesis of acrylonitrile-n-butyl acrylate diblock copolymer

The poly(n-butyl acrylate) (286 parts by weight) synthesized inProduction Example 3, toluene (300 parts by weight), and lead dioxide(0.5 parts by weight) were added to the mercapto group-terminatedpolyacrylonitrile (100 parts by weight) synthesized in ProductionExample 1, and the mixture was stirred at 80° C. for 10 hours in an airatmosphere. ¹H NMR analysis confirmed that an acrylonitrile-n-butylacrylate diblock copolymer in which coupling was performed via disulfidebonds was produced. GPC analysis confirmed that Mw=61,400, Mn=45,400,and Mw/Mn=1.35.

EXAMPLE 15 Synthesis of acrylonitrile-n-butyl acrylate-acrylonitriletriblock copolymer

In a nitrogen atmosphere, dehydrated toluene (300 parts by weight),isophorone diisocyanate (0.70 parts by weight), and dibutyltinbis(isooctyl thioglycolate) (0.05 parts by weight) were added to thepoly(n-butyl acrylate) having mercapto groups at both ends (100 parts byweight) synthesized in Production Example 4, and the mixture was stirredat 80° C. for 8 hours to synthesize poly(n-butyl acrylate) havingisocyanato groups at both ends. The mercapto group-terminatedpolyacrylonitrile (34 parts by weight) synthesized in Production Example1 was added thereinto, and stirring was performed at 80° C. for 16hours. ¹H NMR and GPC analysis confirmed that an acrylonitrile-n-butylacrylate-acrylonitrile triblock copolymer was produced (Mw=127,000,Mn=84,500, and Mw/Mn=1.50).

EXAMPLE 16 Synthesis of acrylonitrile-(n-butyl acrylate/2-methoxyethylacrylate)-acrylonitrile triblock copolymer

In a nitrogen atmosphere, dehydrated toluene (300 parts by weight),isophorone diisocyanate (7.24 parts by weight), and dibutyltinbis(isooctyl thioglycolate) (0.05 parts by weight) were added to then-butyl acrylate-2-methoxyethyl acrylate random copolymer havingmercapto groups at both ends (100 parts by weight) synthesized inProduction Example 5, and the mixture was stirred at 80° C. for 10 hoursto synthesize an n-butyl acrylate/2-methoxyethyl acrylate randomcopolymer having isocyanato groups at both ends. The mercaptogroup-terminated polyacrylonitrile (176 parts by weight) synthesized inProduction Example 1 was added thereinto, and stirring was performed at80° C. for 16 hours. ¹H NMR and GPC analysis confirmed that anacrylonitrile-(n-butyl acrylate/2-methoxyethyl acrylate)-acrylonitriletriblock copolymer was produced (Mw=76,700, Mn=43,600, and Mw/Mn=1.76).

EXAMPLE 17 Synthesis of acrylonitrile-vinyl chloride diblock copolymer

The mercapto group-terminated poly(vinyl chloride) (380 parts by weight)synthesized in Production Example 6 and lead dioxide (1 part by weight)were added to the mercapto group-terminated polyacrylonitrile (100 partsby weight) synthesized in Production Example 1, and the mixture wasmelt-kneaded with a twin-screw extruder (inlet temperature 80° C.;outlet temperature 160° C.) and formed into a strand. The resultantstrand was cut into pellets. The pellets were dried by heating at 80° C.for 30 hours in an air atmosphere. ¹H NMR and GPC analysis confirmedthat an acrylonitrile-vinyl chloride diblock copolymer was produced(Mw=71,100, Mn=49,400, and Mw/Mn=1.44).

EXAMPLE 18 Synthesis of (acrylonitrile/methyl methacrylate)-n-butylacrylate diblock copolymer

In a nitrogen atmosphere, dehydrated toluene (300 parts by weight),hexamethylene diisocyanate (5.78 parts by weight), and dibutyltinbis(isooctyl thioglycolate) (0.05 parts by weight) were added to themercapto group-terminated acrylonitrile/methyl methacrylate randomcopolymer (100 parts by weight) synthesized in Production Example 2, andthe mixture was stirred at 80° C. for 10 hours to produce an isocyanatogroup-terminated acrylonitrile/methyl methacrylate random copolymer. Themercapto group-terminated poly(n-butyl acrylate) (105 parts by weight)synthesized in Production Example 3 was added thereinto, and stirringwas performed at 100° C. for 8 hours in a nitrogen atmosphere. ¹H NMRand GPC analysis confirmed that an (acrylonitrile/methylmethacrylate)-n-butyl acrylate diblock copolymer was produced(Mw=62,900, Mn=45,200, and Mw/Mn=1.39).

EXAMPLE 19 Synthesis of (acrylonitrile/methyl methacrylate)-n-butylacrylate-(acrylonitrile/methyl methacrylate) triblock copolymer

In a nitrogen atmosphere, dehydrated toluene (500 parts by weight),isophorone diisocyanate (0.70 parts by weight), and dibutyltinbis(isooctyl thioglycolate) (0.05 parts by weight) were added to thepoly(n-butyl acrylate) having mercapto groups at both ends (100 parts byweight) synthesized in Production Example 4, and the mixture was stirredat 80° C. for 8 hours to synthesize poly(n-butyl acrylate) havingisocyanato groups at both ends. The mercapto group-terminatedacrylonitrile-methyl methacrylate diblock copolymer (92 parts by weight)synthesized in Production Example 2 was added thereinto, and stirringwas performed at 80° C. for 16 hours. ¹H NMR and GPC analysis confirmedthat an (acrylonitrile/methyl methacrylate)-n-butylacrylate-(acrylonitrile/methyl methacrylate) triblock copolymer wasproduced (Mw=122,100, Mn=78,900, and Mw/Mn=1.55).

EXAMPLE 20 Synthesis of (acrylonitrile/methyl methacrylate)-(n-butylacrylate/2-methoxyethyl acrylate)-(acrylonitrile/methyl methacrylate)triblock copolymer

In a nitrogen atmosphere, dehydrated toluene (500 parts by weight),isophorone diisocyanate (7.22 parts by weight), and dibutyltinbis(isooctyl thioglycolate) (0.05 parts by weight) were added to then-butyl acrylate/2-methoxyethyl acrylate random copolymer havingmercapto groups at both ends (100 parts by weight) synthesized inProduction Example 5, and the mixture was stirred at 80° C. for 10 hoursto synthesize an n-butyl acrylate/2-methoxyethyl acrylate randomcopolymer having isocyanato groups at both ends. The mercaptogroup-terminated acrylonitrile/methyl methacrylate random copolymer (474parts by weight) synthesized in Production Example 2 was addedthereinto, and stirring was performed at 80° C. for 15 hours. ¹H NMR andGPC analysis confirmed that an (acrylonitrile/methylmethacrylate)-(n-butyl acrylate/2-methoxyethylacrylate)-(acrylonitrile/methyl methacrylate) triblock copolymer wasproduced (Mw=57,700, Mn=35,500, and Mw/Mn=1.63).

EXAMPLE 21 Synthesis of (acrylonitrile/methyl methacrylate)-vinylchloride diblock copolymer

The mercapto group-terminated poly(vinyl chloride) (141 parts by weight)synthesized in Production Example 6, tetrahydrofuran (300 parts byweight), and lead dioxide (0.5 parts by weight) were added to themercapto group-terminated acrylonitrile/methyl methacrylate randomcopolymer (100 parts by weight) synthesized in Production Example 2, andthe mixture was stirred at 80° C. for 10 hours in an air atmosphere. ¹HNMR analysis confirmed that an (acrylonitrile/methyl methacrylate)-vinylchloride diblock copolymer in which coupling was performed via disulfidebonds was produced. GPC analysis confirmed that Mw=68,200, Mn=46,200,and Mw/Mn=1.48.

EXAMPLE 22 Synthesis of acrylonitrile-n-butyl acrylate-acrylonitriletriblock copolymer

In a nitrogen atmosphere, dehydrated toluene (300 parts by weight),allyl isocyanate (0.5 parts by weight), and dibutyltin bis(isooctylthioglycolate) (0.02 parts by weight) were added to the poly(n-butylacrylate) having mercapto groups at both ends (100 parts by weight)synthesized in Production Example 4, and the mixture was stirred at 80°C. for 5 hours. Dibutyltin bis(isooctyl thioglycolate) and excess allylisocyanate were removed through a silica gel column (50 parts byweight), and toluene was removed by distillation. Thereby, poly(n-butylacrylate) having allyl groups at both ends via thiourethane bonds wasproduced. NMR analysis confirmed that the introduction rate of allylgroups was 89% on the both-ends basis.

On the other hand, the polyacrylonitrile (100 parts by weight)synthesized in Production Example 7 was dissolved in dimethylformamide(300 parts by weight), and 3-isocyanatopropyldimethylsilane (1.4 partsby weight) and dibutyltin bisacetylacetonate (0.01 parts by weight) wereadded thereinto, followed by stirring at 80° C. for 6 hours. Thereaction solution was concentrated and reprecipitated with methanol.Polyacrylonitrile having a hydrosilyl group at one end was therebyproduced. NMR analysis confirmed that the introduction rate ofhydrosilyl groups was 88% on the single-end basis.

Dimethylformamide (300 parts by weight) was added to a mixture of theresultant polyacrylonitrile having the hydrosilyl group at one end (100parts by weight) and the poly(n-butyl acrylate) having the allyl groupat both ends, and a 3% by weight xylene solution ofplatinum-1,3-divinyltetramethyldisiloxane complex (0.3 parts by weight)was added thereinto. After the mixture was matured at 80° C. for 8hours, dimethylformamide was removed by distillation. Toluene (200 partsby weight) was added thereto, and insolubles were removed. The solutionwas poured into methanol (500 parts by weight), and reprecipitation wasperformed. Thereby, an acrylonitrile-n-butyl acrylate-acrylonitriletriblock copolymer was produced (Mw=128,800, Mn=73,200, and Mw/Mn=1.76).

COMPARATIVE PRODUCTION EXAMPLE 1 Synthesis of acrylonitrile/n-butylacrylate random copolymer

Into a 2 L reactor equipped with an agitator, a thermometer, a nitrogengas inlet tube, a dropping funnel, and a reflux condenser, was placed600 g of distilled water, 0.71 g of sodium dodecyl sulfate as anemulsifier, and as monomers, 70 g of acrylonitrile and 30 g of n-butylacrylate, and the reactor was nitrogen-purged while the reaction mixturewas being stirred at 80° C. Next, 1.6 g of 4,4′-azobis(4-cyanovalericacid) as a polymerization initiator together with 30 g of distilledwater was added into the reactor, and a reaction was initiated. Stirringwas performed at 80° C. for 10 hours, and an acrylonitrile/n-butylacrylate random copolymer was produced with a conversion rate ofmonomers of 89%. GPC measurement confirmed that Mw=472,000, Mn=214,000,and Mw/Mn=2.21.

EXAMPLE 23 Polycarbonate thermoplastic resin composition

A polycarbonate resin LEXAN 141R-111 (manufactured by GE Plastics Japan,Ltd.) (100 parts by weight) as a thermoplastic resin, IRGANOX HP2215(manufactured by Ciba Specialty Chemicals) (0.5 parts by weight) as astabilizer, and the block copolymer synthesized in Example 1 (6 parts byweight) were compounded. The resultant composition was extrusion-kneadedat 280° C. with a twin-screw extruder (32 mm, L/D=25.5) and pelletized.The resultant pellets were dried at 80° C. for 15 hours, and injectionmolding was then performed at 280° C. to form a molded object (¼ inchthick) for evaluating physical properties. The Izod impact strength at0° C. and flame retardancy of the resultant molded object wereevaluated. The results thereof are shown in Table 1 below.

Additionally, Izod impact strength was measured according to ASTMD256-56, using V-notched specimens, and average values measured at n=5were adopted. Flame retardancy was measured according to UL-94 standard.

EXAMPLES 24 TO 44

Molded objects were formed as in Example 23 except that the blockcopolymers synthesized in Examples 2 to 22 were used instead of theblock copolymer synthesized in Example 1. The Izod impact strength at 0Cand flame retardancy were evaluated. The results thereof are shown inTable 1.

COMPARATIVE EXAMPLE 1

A molded object was formed as in Example 23 except that the randomcopolymer synthesized in Comparative Production Example 1 was usedinstead of the block copolymer synthesized in Example 1. The Izod impactstrength at 0° C. and flame retardancy were evaluated. The resultsthereof are shown in Table 1.

COMPARATIVE EXAMPLE 2

A molded object was formed as in Example 23 without compounding theblock copolymer synthesized in Example 1. The Izod impact strength at 0Cand flame retardancy were evaluated. The results thereof are shown inTable 1.

TABLE 1 Izod impact strength Flame Example Composition (kJ/m²)retardancy Example 23 Example 1 10.5 V-2 Example 24 Example 2 9.7 V-2Example 25 Example 3 11.4 V-2 Example 26 Example 4 11.5 V-1 Example 27Example 5 15.2 V-1 Example 28 Example 6 16.1 V-1 Example 29 Example 711.8 V-1 Example 30 Example 8 11.8 V-1 Example 31 Example 9 14.9 V-1Example 32 Example 10 12.5 V-1 Example 33 Example 11 10.1 V-0 Example 34Example 12 10.0 V-2 Example 35 Example 13 14.7 V-2 Example 36 Example 149.1 V-2 Example 37 Example 15 13.3 V-2 Example 38 Example 16 12.0 V-1Example 39 Example 17 7.2 V-0 Example 40 Example 18 8.8 V-2 Example 41Example 19 17.1 V-1 Example 42 Example 20 16.1 V-1 Example 43 Example 217.7 V-0 Example 44 Example 22 10.2 V-1 Comparative Comparative 4.1 notVExample 1 Production Example 1 Comparative — 2.9 notV Example 2

As is evident from Table 1, the thermoplastic resin compositions inwhich the block copolymers of the present invention are compounded areexcellent in impact strength at low temperatures and flame retardancy.

EXAMPLE 45 Polyester Thermoplastic Resin Composition

A poly(butylene terephthalate) resin DURANEX 2002 (manufactured byPolyplastic Co., Ltd.) (80 parts by weight) as a thermoplastic resin,Topanol Calif. (manufactured by Lipre Co., Ltd.) (0.3 parts by weight)as a phenolic antioxidant, Adekasutabu PEP-36 (manufactured by AsahiDenka Co., Ltd.) (0.3 parts by weight) as a HALS, and the blockcopolymer synthesized in Example 1 (20 parts by weight) were compounded.Using a twin-screw extruder (32 mm, L/D=25.5), the resultant compositionwas extrusion-kneaded at 245° C. and pelletized. The resultant pelletswere dried at 80° C. for 15 hours, and injection molding was thenperformed at 250° C. to form a molded object (¼ inch thick) forevaluating physical properties. The Izod impact strength at 0° C. of theresultant molded object was evaluated. The result thereof is shown inTable 2 below.

EXAMPLES 46 TO 66

Molded objects were formed as in Example 45 except that the blockcopolymers synthesized in Examples 2 to 22 were used instead of theblock copolymer synthesized in Example 1. The Izod impact strength at 0°C. of each resultant molded object was evaluated. The results thereofare shown in Table 2.

COMPARATIVE EXAMPLE 3

A molded object was formed as in Example 45 except that the randomcopolymer synthesized in Comparative Production Example 1 was usedinstead of the block copolymer synthesized in Example 1. The Izod impactstrength at 0° C. was evaluated. The result thereof is shown in Table 2.

COMPARATIVE EXAMPLE 4

A molded object was formed as in Example 45 without compounding theblock copolymer synthesized in Example 1. The Izod impact strength at 0°C. was evaluated. The result thereof is shown in Table 2.

TABLE 2 Izod impact strength Example Composition (kJ/m²) Example 45Example 1 9.6 Example 46 Example 2 8.5 Example 47 Example 3 9.3 Example48 Example 4 10.1 Example 49 Example 5 11.5 Example 50 Example 6 11.8Example 51 Example 7 10.1 Example 52 Example 8 9.1 Example 53 Example 912.5 Example 54 Example 10 10.9 Example 55 Example 11 9.1 Example 56Example 12 8.3 Example 57 Example 13 11.1 Example 58 Example 14 9.0Example 59 Example 15 10.8 Example 60 Example 16 10.7 Example 61 Example17 8.1 Example 62 Example 18 8.3 Example 63 Example 19 13.2 Example 64Example 20 13.7 Example 65 Example 21 7.8 Example 66 Example 22 9.3Comparative Comparative 3.1 Example 3 Production Example 1 Comparative —2.8 Example 4

As is evident from Table 2, the thermoplastic resin compositions inwhich the block copolymers of the present invention are compounded areexcellent in impact strength at low temperatures.

EXAMPLE 67 Elastomer Composition

An acrylic rubber AR42W (manufactured by ZEON Corporation) (100 parts byweight) and the block copolymer synthesized in Example 1 (100 parts byweight) were compounded and melt-kneaded with a Laboplastomill at 190°C. After 3 minutes, as a crosslinking agent, ammonium benzoate (3 partsby weight) was added thereinto, and melt-kneading was further performedwith the Laboplastomill at 190° C. The resultant sample block wasthermopress-molded at 190° C., and molded objects with a thickness of 2mm for evaluating physical properties were formed. The resultant moldedobjects were crosslinked by heating at 150° C. for 2 hours. With respectto the molded objects, tensile strength at break and elongation at breakat 0° C., and oil resistance were evaluated. The results thereof areshown in Table 3 below.

Additionally, tensile strength at break and elongation at break weremeasured according to JIS K6251, at 0° C. With respect to oilresistance, according to JIS C232, molded objects were immersed intransformer oil B at 70° C. for 4 hours, and the oil resistance wasmeasured based on the rates of change in weight.

EXAMPLES 68 TO 88

Molded objects were formed as in Example 67 except that the blockcopolymers synthesized in Examples 2 to 22 were used instead of theblock copolymers synthesized in Example 1. The tensile strength at breakand elongation at break at 0° C., and oil resistance were evaluated. Theresults thereof are shown in Table 3.

COMPARATIVE EXAMPLE 5

Molded objects were formed as in Example 67 except that the randomcopolymer synthesized in Comparative Production Example 1 was usedinstead of the block copolymer synthesized in Example 1. The tensilestrength at break and elongation at break at 0° C., and oil resistancewere evaluated. The results thereof are shown in Table 3.

COMPARATIVE EXAMPLE 6

Molded objects were formed as in Example 67 without compounding theblock copolymer synthesized in Example 1. The tensile strength at breakand elongation at break at 0° C., and oil resistance were evaluated. Theresults thereof are shown in Table 3.

TABLE 3 Tensile strength at Elongation Oil break at break resistanceExample Composition (MPa) (%) (%) Example 67 Example 1 4.1 340 11Example 68 Example 2 5.2 310 9 Example 69 Example 3 4.8 300 7 Example 70Example 4 3.5 420 4 Example 71 Example 5 7.1 220 12 Example 72 Example 66.6 230 11 Example 73 Example 7 5.9 280 10 Example 74 Example 8 4.5 27010 Example 75 Example 9 6.0 240 6 Example 76 Example 10 6.9 250 7Example 77 Example 11 8.1 200 4 Example 78 Example 12 4.0 300 13 Example79 Example 13 5.0 270 14 Example 80 Example 14 3.7 360 14 Example 81Example 15 4.2 350 13 Example 82 Example 16 4.5 330 11 Example 83Example 17 3.0 470 8 Example 84 Example 18 3.9 370 15 Example 85 Example19 4.0 370 14 Example 86 Example 20 6.2 210 16 Example 87 Example 21 3.3440 8 Example 88 Example 22 3.7 420 11 Comparative Comparative 1.4 50028 Example 5 Production Example 1 Comparative — 1.6 490 21 Example 6

As is evident from Table 3, the elastomer compositions in which theblock copolymers of the present invention are compounded are excellentin strength at low temperatures and oil resistance.

INDUSTRIAL APPLICABILITY

As described above, in accordance with the present invention, it ispossible to produce (meth)acrylonitrile-based block copolymers which areexcellent in heat resistance, weatherability, oil resistance, flameretardancy, and low-temperature resistance. The block copolymers can beprepared by water-based polymerization and the purification step can besimplified, and thus economical production is enabled. The thermoplasticresin compositions and elastomer compositions containing the blockcopolymers can be used in various applications, such as films, sheets,tapes, hoses, tubes, gaskets, packings, grips, containers, variousmolded objects, sealants, damping materials, pressure-sensitiveadhesives, adhesives, coating materials, potting materials, andtextiles.

1. A block copolymer prepared by coupling of the block copolymer,wherein the block copolymer comprises a polymer block (A) and a polymerblock (B), the block copolymer being produced by forming the polymerblock (A) by reversible addition-fragmentation chain transferpolymerization in the presence of a thiocarbonylthio group-containingcompound, and then by forming the polymer block (B), wherein the polymerblock (A) is prepared by (co)polymerizing 50% to 100% by weight of atleast one monomer selected from the group consisting of acrylonitrileand methacrylonitrile and 50% to 0% by weight of at least one monomerselected from the group consisting of methacrylate esters, styrene, andα-methylstyrene, and the polymer block (B) is prepared by(co)polymerizing at least one monomer selected from the group consistingof acrylic acid, methacrylic acid, acrylate esters, methacrylate esters,vinyl acetate, styrene, α-methylstyrene, butadiene, isoprene, and vinylchloride, wherein the thiocarbonylthio group of the block copolymer isconverted into a mercapto group or a mercaptide group, and wherein saidcoupling is performed by a reaction of the mercapto group of the blockcopolymer or the mercaptide group of the block copolymer with anothermercapto group of the block copolymer or another mercaptide group of theblock copolymer.
 2. The block copolymer according to claim 1, whereinthe thiocarbonylthio group-containing compound is at least one compoundselected from the group consisting of a compound represented by generalformula (1):

(wherein R1 is a p-valent organic group of 1 or more carbon atoms whichmay contain one of nitrogen, oxygen, sulfur, halogen, silicon,phosphorus, and metal atoms, or which may be a polymer; Z1 is a hydrogenatom, halogen atom, or monovalent organic group of 1 or more carbonatoms which may contain one of nitrogen, oxygen, sulfur, halogen,silicon, and phosphorus atoms, or which may be a polymer; when pluralZ1s are present, the plural Z1s may be the same or different; and p isan integer of 1 or more), and a compound represented by general formula(2):

(wherein R2 is a monovalent organic group of 1 or more carbon atomswhich may contain one of nitrogen, oxygen, sulfur, halogen, silicon,phosphorus, and metal atoms, or which may be a polymer; Z2 is an oxygenatom (when q=2), sulfur atom (when q=2), nitrogen atom (when q=3), orq-valent organic group of 1 or more carbon atoms which may contain oneof nitrogen, oxygen, sulfur, halogen, silicon, and phosphorus atoms, orwhich may be a polymer; plural R2s may be the same or different; and qis an integer of 2 or more).
 3. The block copolymer according to claim1, wherein the thiocarbonylthio group-containing compound is a compoundrepresented by general formula (3):

(wherein R2 is a monovalent organic group of 1 or more carbon atomswhich may contain one of nitrogen, oxygen, sulfur, halogen, silicon,phosphorus, and metal atoms, or which may be a polymer; and Z1 is ahydrogen atom, halogen atom, or monovalent organic group of 1 or morecarbon atoms which may contain one of nitrogen, oxygen, sulfur, halogen,silicon, and phosphorus atoms, or which may be a polymer).
 4. The blockcopolymer according to claim 1, wherein the thiocarbonylthio group ofthe thiocarbonylthio group-containing block copolymer is converted intothe mercapto group or the mercaptide group by a reaction with aprocessing agent comprising at least one compound selected from thegroup consisting of bases, acids, and hydrogen-nitrogen bond-containingcompounds.
 5. The block copolymer according to claim 4, wherein theprocessing agent is at least one compound selected from the groupconsisting of ammonia, primary amine compounds with a boiling point of100° C. or less, secondary amine compounds with a boiling point of 100°C. or less, and hindered amine light stabilizers (HALSs).
 6. The blockcopolymer according to claim 1, wherein said coupling is performed bythe formation of disulfide bonds using an oxidizing agent.
 7. The blockcopolymer according to claim 1, wherein a functional group is introducedinto the mercapto group or the mercaptide group for performing saidcoupling.
 8. The block copolymer according to claim 7, wherein saidcoupling is performed using at least one functional group selected fromthe group consisting of a crosslinkable silyl group, unsaturated groups,and a hydroxyl group.
 9. The block copolymer according to claim 1,wherein the polymer block (A) is prepared by polymerizing 80% to 100% byweight of at least one monomer selected from the group consisting ofacrylonitrile and methacrylonitrile and 20% to 0% by weight of at leastone monomer selected from the group consisting of methacrylate esters,styrene, and α-methylstyrene.
 10. The block copolymer according to claim9, wherein the polymer block (A) is prepared by polymerizing 100% byweight of at least one monomer selected from the group consisting ofacrylonitrile and methacrylonitrile.
 11. The block copolymer accordingto claim 1, wherein the polymer block (B) is prepared by polymerizing anacrylate ester.
 12. The block copolymer according to claim 1, whereinthe molecular weight distribution of the polymer block (A) is 1.8 orless, the molecular weight distribution being determined by gelpermeation chromatography analysis.
 13. The block copolymer according toclaim 1, wherein the molecular weight distribution of the blockcopolymer comprising the polymer block (A) and the polymer block (B) is1.8 or less, the molecular weight distribution being determined by gelpermeation chromatography analysis.
 14. The block copolymer according toclaim 1, wherein the glass transition temperature of the polymer block(A) is 50° C. or more.
 15. The block copolymer according to claim 1,wherein the glass transition temperature of the polymer block (B) is 30°C. or less.
 16. A thermoplastic resin composition comprising athermoplastic resin and the block copolymer according to claim
 1. 17. Anelastomer composition comprising a synthetic rubber and the blockcopolymer according to claim 1.